Substituted 2-benzoyl-cyclohexan-1,3-diones with herbicidal effect

ABSTRACT

The invention relates to 2-benzoylcyclohexane-1,3-diones of the formula I                    
     where 
     R 1 , R 2  are each hydrogen, nitro, halogen, cyano, thiocyanato, alkyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, —OR 5 , —OCOR 6 , —OSO 2 R 6 , —SH, —S(O) n R 7 , —SO 2 OR 5 , —SO 2 NR 5 R 8 , —NR 8 SO 2 R 6  or —NR 8 COR 6 ; 
     R 3  is hydrogen, cyano, alkyl, haloalkyl, —OR 7 , —SR 7  or —NR 7 R 10 ; 
     R 4  is hydrogen, substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, —COR 9 , —CO 2 R 9 , —COSR 9  or —CONR 8 R 9 ; 
     X is oxygen or NR 8 ; 
     n is 0, 1 or 2; 
     R 5  is hydrogen, alkyl, haloalkyl, alkoxyalkyl, alkenyl or alkynyl; 
     R 6  is alkyl or haloalkyl; 
     R 7  is alkyl, haloalkyl, alkoxyalkyl, alkenyl or alkynyl; 
     R 8  is hydrogen or alkyl; 
     R 9  is alkyl, alkenyl, alkynyl, phenyl or benzyl; 
     R 10  is alkyl, haloalkyl, alkenyl or alkynyl; 
     Q is a cyclohexane-1,3-dione ring with or without substitution attached in position 2; 
     and agriculturally useful salts thereof; 
     to processes and intermediates for preparing the compounds of the formula I; to compositions comprising them; and to the use of these derivatives or compositions comprising them for controlling undesirable plants.

This application is a 370 of PCT/EP97/07214 filed Dec. 19, 1997.

The present invention relates to substituted2-benzoyl-cyclohexane-1,3-diones of the formula I

where:

R¹ and R² are are each hydrogen, nitro, halogen, cyano, thiocyanato,C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl,C₂-C₆-alkynyl, —OR⁵, —OCOR⁶, —OSO₂R⁶, —SH, —S(O)_(n)R⁷, —SO₂OR⁵,—SO₂NR⁵R⁸, —NR⁸SO₂R⁶ or —NR⁸COR⁶;

R³ is hydrogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl, —OR⁷, —SR⁷ or—NR⁷R¹⁰;

R⁴ is hydrogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-alkenyl,C₄-C₆-cycloalkenyl, C₃-C₆-alkynyl, —COR⁹, —CO₂R⁹, —COSR⁹ or —CONR⁸R⁹,where the alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicalsmentioned and R⁹ of the radicals —COR⁹, —CO₂R⁹, —COSR⁹ and —CONR⁸R⁹ maybe partially or fully halogenated and/or carry one to three of thefollowing groups:

hydroxyl, mercapto, amino, cyano, R¹⁰, —OR¹⁰, —SR¹⁰, —NR⁸R¹⁰, ═NOR¹⁰,—OCOR¹⁰, —SCOR¹⁰, —NR⁸COR¹⁰, —CO₂R¹⁰, —COSR¹⁰, —CONR⁸R¹⁰,C₁-C₄-alkyliminooxy, C₁-C₄-alkoxyamino, C₁-C₄-alkylcarbonyl,C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, C₁-C₄-alkylsulfonyl, heterocyclyl,heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy andhetaryloxy, where the last eight radicals mentioned may in turn besubstituted;

X is oxygen or NR⁸:

n is 0, 1 or 2;

R⁵ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₂-C₆-alkyl,C₃-C₆-alkenyl or C₃-C₆-alkynyl;

R⁶ is C₁-C₆-alkyl or C₁-C₆-haloalkyl;

R⁷ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₂-C₆-alkyl,C₃-C₆-alkenyl or C₃-C₆-alkynyl;

R⁸ is hydrogen or C₁-C₆-alkyl;

R⁹ is C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, phenyl or benzyl;

R¹⁰ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl;

Q is a cyclohexane-1,3-dione ring attached in position 2 with or withoutsubstitution;

and agriculturally useful salts thereof.

The invention additionally relates to processes and intermediates forpreparing compounds of the formula I, to compositions comprising them,and to the use of the compounds of the formula I or of compositionscomprising them for controlling harmful plants.

2-Benzoylcyclohexane-1,3-diones are known from the literature, forexample from EP-A 278 742, EP-A 298 680, EP-A 320 864 and WO 96/14285.

However, the herbicidal properties of these prior art compounds andtheir compatibility with crop plants are not entirely satisfactory.

It is an object of the present invention to provide novel, in particularherbicidally active, compounds having improved properties.

We have found that this object is achieved by the2-benzoyl-cyclohexane-1,3-diones of the formula I and their herbicidalaction.

Furthermore, the invention provides herbicidal compositions comprisingthe compounds I and having a very good herbicidal activity.Additionally, the invention provides processes for preparing thesecompositions and methods for controlling undesirable vegetation usingthe compounds I.

The present invention also provides stereoisomers of the compounds ofthe formula I. Pure stereoisomers and also mixtures thereof areincluded.

The compounds of the formula I contain a carbon-nitrogen double bond andare therefore present as E isomers or Z isomers or as E/Z isomermixtures. Furthermore, the compounds of the formula I may containfurther carbon-carbon or carbon-nitrogen double bonds. The inventionprovides the pure geometric isomers and also mixtures thereof.

Depending on the substitution pattern, the compounds of the formula Imay contain one or more chiral centers and, if this is the case, arepresent as mixtures of enantiomers or diastereomers. The inventionprovides the pure enantiomers or diastereomers and also mixturesthereof.

The compounds of the formula I may also be present in the form of theiragriculturally useful salts, the kind of salt generally not beingimportant. The salts of those cations or the acid additon salts of thoseacids whose cations or anions, respectively, do not adversely affect theherbicidal activity of the compounds I are generally suitable.

Suitable cations are in particular ions of the alkali metals, preferablylithium, sodium and potassium, of the alkaline earth metals, preferablycalcium and magnesium, and of the transition metals, preferablymanganese, copper, zinc and iron, and ammonium, where, if desired, oneto four hydrogen atoms may be replaced by C₁-C₄-alkyl orhydroxyl-C₁-C₄-alkyl and/or one phenyl or benzyl, preferablydiisopropylammonium, tetramethylammonium, tetrabutylammonium,trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions,preferably tri(C₁-C₄-alkyl)sulfonium and sulfoxonium ions, preferablytri(C₁-C₄-alkyl)sulfoxonium.

Anions of usable acid addition salts are primarily chloride, bromide,fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogenphosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate,hexafluorophosphate, benzoate and the anions of C₁-C₄-alkanoic acids,preferably formate, acetate, propionate and butyrate.

Emphasis is given to compounds of the formula I according to theinvention where the variable Q is a cyclohexane-1,3-dione ring of theformula II linked in position 2

where II also represents the tautomeric formulae II′ and II″,

where

R¹¹, R¹², R¹⁴ and R¹⁶ are each hydrogen or C₁-C₄-alkyl;

R¹³ is hydrogen, C₁-C₄-alkyl or C₃-C₄-cycloalkyl, where the last twogroups may carry one to three of the following substituents: halogen,C₁-C₄-alkylthio or C₁-C₄-alkoxy; or

is tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl,tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl,tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl; 1,3-dioxan-2-yl,1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl or1,3-dithian-2-yl, where the last 6 radicals mentioned may be substitutedby one to three C₁-C₄-alkyl radicals;

R¹⁵ is hydrogen, C₁-C₄-alkyl or C₁-C₆-alkoxycarbonyl; or

R¹³ and R¹⁶ together form a π-bond or a three- to six-memberedcarbocylic ring; or

the CR¹³R¹⁴ unit is replaced by C═O.

Emphasis is also given to compounds of the formula I according to theinvention where

R⁴ is hydrogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-alkenyl,C₄-C₆-cycloalkenyl, C₃-C₆-alkynyl, —COR⁹, —CO₂R⁹, —COSR⁹ or —CONR⁸R⁹where the alkyl, cycloalkyl, alkenyl-, cycloalkenyl and alkynyl radicalsmentioned and R⁹ of the radicals —COR⁹, —CO₂R⁹, —COSR⁹ and —CONR⁸R⁹ maybe partially or fully halogenated and/or carry one to three of thefollowing groups:

hydroxyl, mercapto, amino, cyano, R¹⁰, —OR¹⁰, —SR¹⁰, —NR⁸R¹⁰, ═NOR¹⁰,—OCOR¹⁰, —SCOR¹⁰, —NR⁸COR¹⁰, —CO₂R¹⁰, —COSR¹⁰, —CONR⁸R¹⁰,C₁-C₄-alkyliminooxy, C₁-C₄-alkoxyamino, C₁-C₄-alkylcarbonyl,C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, C₁-C₄-alkylsulfonyl, heterocyclyl,heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy andhetaryloxy, where the last eight radicals mentioned may in turn bepartially or fully halogenated and/or carry one to three radicals fromthe following group:

nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkoxycarbonyl.

The organic moieties mentioned for the substituents R¹-R¹⁶ or asradicals on phenyl, hetaryl and heterocylyl rings represent collectiveterms for lists of the individual group members. All hydrocarbon chains,ie. all alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, alkoxy, haloalkoxy,alkyliminooxy, alkoxyamino, alkylthio, alkylsulfonyl, alkylcarbonyl,alkoxycarbonyl, alkoxyalkoxycarbonyl, alkenyl, cycloalkenyl and alkynylmoieties, may be straight-chain or branched. Unless stated otherwise,preference is given to halogenated substituents carrying one to fiveidentical or different halogens. Halogen is in each case fluorine,chlorine, bromine or iodine.

Furthermore, the following moities represent, for example:

C₂-C₄-alkyl: ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,2-methylpropyl and 1,1-dimethylethyl;

C₁-C₄-alkyl and the alkyl moieties of C₁-C₄-alkylcarbonyl: C₂-C₄-alkylas mentioned above, and methyl;

C₂-C₆-alkyl, and the alkyl moieties of C₁-C₆-alkoxy-C₂-C₆-alkyl:C₂-C₄-alkyl as mentioned above, and pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1-ethyl-1-methylpropyl and 1-ethyl-3-methylpropyl;

C₁-C₆-alkyl and the alkyl moieties of C₁-C₆-alkoxy-C₁-C₆-alkyl:C₂-C₆-alkyl as mentioned above, and methyl;

C₁-C₄-haloalkyl: a C₁-C₄-alkyl radical as mentioned above which ispartially or fully substituted by fluorine, chlorine, bromine and/oriodine, ie. for example chloromethyl, dichloromethyl, trichloromethyl,fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl,dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl,2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl,2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl,2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl,2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl,3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl,1-(fluoromethyl)-2-fluoroethyl 1-(chloromethyl)-2-chloroethyl,1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyland nonafluorobutyl;

C₁-C₆-haloalkyl: C₁-C₄-haloalkyl as mentioned above, and 5-fluoropentyl,5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl,6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl anddodecafluorohexyl;

C₁-C₄-alkoxy and the alkoxy moieties of C₁-C₄-alkoxyamino,C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl and C₁-C₄-alkoxycarbonyl: methoxy,ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy,2-methylpropoxy and 1,1-dimethylethoxy;

C₁-C₆-alkoxy and the alkoxy moieties of C₁-C₆-alkoxy-C₁-C₆-alkyl,C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl and C₁-C₆-alkoxycarbonyl: C₁-C₄-alkoxyas mentioned above, and pentoxy, 1-methylbutoxy, 2-methylbutoxy,3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy,2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy,2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy,1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy,2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy,1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxyand 1-ethyl-2-methylpropoxy;

C₁-C₄-haloalkoxy: a C₁-C₄-alkoxy radical as mentioned above which ispartially or fully subsstituted by fluorine, chlorine, bromine and/oriodine, ie. for example fluoromethoxy, difluoromethoxy,trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy,2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy,2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chlor-2-fluoroethoxy,2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy,3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy,3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy,2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy,2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy,1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy,1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy,4-bromobutoxy and nonafluorobutoxy;

C₁-C₄-alkylthio: methylthio, ethylthio, propylthio, 1-methylethylthio,butylthio, 1-methylpropylthio, 2-methylpropylthio and1,1-dimethylethylthio;

C₁-C₄-alkylsulfonyl (C₁-C₄-alkyl-S(═O)₂—): methylsulfonyl,ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl,1-methylpropylsulfonyl, 2-methylpropylsulfonyl and1,1-dimethylethylsulfonyl;

C₁-C₄-alkyliminooxy: methyliminooxy, ethyliminooxy, 1-propyliminooxy,2-propyliminooxy, 1-butyliminooxy and 2-butyliminooxy;

C₃-C₆-alkenyl: prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl,buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl,2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl,penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl,1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl,1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl,1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl,1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl,1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl,1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl,hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent-1-en-1-yl,2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl,1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl,4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl,3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl,2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl,1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl,1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl,1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl,1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl,2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl,2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl,3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl,1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl,2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl,1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl,1-ethyl-2-methylprop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl;

C₂-C₆-alkenyl: C₃-C₆-alkenyl as mentioned above, and ethenyl;

C₃-C₆-alkynyl: prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn-1-yl,but-1-yn-3-yl, but-1-yn-4-yl but-2-yn-1-yl, pent-1-yn-1-yl,pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl, pent-2-yn-1-yl,pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl,3-methylbut-1-yn-4-yl, hex-1-yn-1-yl, hex-1-yn-3-yl, hex-1-yn-4-yl,hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl, hex-2-yn-4-yl,hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-1-yl, hex-3-yn-2-yl,3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl,3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yland 4-methylpent-2-yn-5-yl;

C₂-C₆-alkynyl: C₃-C₆-alkynyl as mentioned above, and ethynyl:

C₃-C₆-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;

C₄-C₆-cycloalkenyl: cyclobuten-1-yl, cyclobuten-3-yl, cyclopenten-1-yl,cyclopenten-3-yl, cyclopenten-4-yl, cyclohexen-1-yl, cyclohexen-3-yl andcyclohexen-4-yl;

heterocyclyl and the heteroclyl [sic] radicals in heterocyclyloxy:three- to seven-membered saturated or partially unsaturated mono- orpolycyclic heterocycles containing one to three hetero atoms selectedfrom a group consisting of oxygen, nitrogen and sulfur, such asoxiranyl, oxetan-3-yl, thietan-3-yl, 2-tetrahydrofuranyl,3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl,2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl,5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl,2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl,4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl,1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl,1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl,1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl,1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl,2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,3-dihydrofuran-4-yl,2,3-dihydrofuran-5-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl,2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,3-dihydrothien-4-yl,2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl,2,3-dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl,2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl,2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl,2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl,4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl,2,5-dihydroisoxazol-3-yl, 2,5-dihydroisoxazol-4-yl,2,5-dihydroxazol-5-yl, 2,3-dihydroisothiazol-3-yl,2,3-dihydroisothiazol-4-yl, 2,3-dihydroisothiazol-5-yl,4,5-dihydroisothiazol-3-yl, 4,5-dihydroisothiazol-4-yl,4,5-dihydroisothiazol-5-yl, 2,5-dihydroisothiazol-3-yl,2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl,2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl,2,3-dihydropyrazol-5-yl, 4,5-dihydropyrazol-3-yl,4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl,2,5-dihydropyrazol-3-yl, 2,5-dihydropyrazol-4-yl,2,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-4-yl,2,3-dihydrooxazol-5-yl, 4,5-dihydrooxazol-2-yl, 4,5-dihydrooxazol-4-yl,4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4-yl,2,5-dihydrooxazol-5-yl, 2,3-dihydrothiazol-2-yl,2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl,4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl,4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl,2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl,2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl,2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2-yl,4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl,2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazol-4-yl,2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl,3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl,4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl,4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl,1,3,5-tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl,1,3-dihydrooxazin-2-yl, 1,3-dioxan-2-yl, 1,3-dithian-2-yl,2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl,2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl,4-tetrahydrothiopyranyl, 1,3-dioxolan-2-yl, 1,3-dithiolan-2-yl,3,4,5,6-tetrahydropyridin-2-yl, 4H-1,3-thiazin-2-yl,4H-3,1-benzothiazin-2-yl, 1,1-dioxo-2,3,4,5-tetrahydrothien-2-yl,2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxazin-3-yl,1,3-dihydrooxazin-2-yl,

hetaryl and the hetaryl radicals in hetaryloxy:

aromatic mono- or polycyclic radicals which, in addition to carbon ringmembers, may contain one to four nitrogen atoms or one to three nitrogenatoms and one oxygen or one sulfur atom or one oxygen or one sulfuratom, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl,3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl,2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl,5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl,1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl,1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl,3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl,5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl,1,2,4,5-tetrazin-3-yl, and the corresponding benzo-fused derivatives.

All phenyl and hetaryl rings are preferably unsubstituted or carry oneto three halogens and/or one or two radicals from the following group:nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy ormethoxycarbonyl.

Preferred with a view to the use of the compounds of the formula Iaccording to the invention as herbicides are those compounds where thevariables have the following meanings, in each case either on their ownor in combination:

R¹ is nitro, halogen, cyano, thiocyanato, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, —OR⁵ or—S(O)_(n)R⁷;

particularly preferably nitro, halogen such as, for example, fluorine,chlorine or bromine, C₁-C₆-haloalkyl, —OR⁵ or —SO₂R⁷ such as, forexample, methylsulfonyl, ethylsulfonyl or difluoromethylsulfonyl;especially preferably nitro, fluorine, chlorine, bromine,trifluoromethyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl ordifluoromethylsulfonyl;

R² is hydrogen, nitro, halogen, cyano, thiocyanato, C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,—OR⁵ or —S(O)_(n)R⁷;

particularly preferably hydrogen, nitro, halogen such as, for example,fluorine, chlorine or bromine, C₁-C₆-alkyl such as, for example, methylor ethyl, C₁-C₆-haloalkyl, —OR⁵ or —SO₂R⁷ such as, for example,methylsulfonyl, ethylsulfonyl or difluoromethylsulfonyl;

especially preferably nitro, fluorine, chlorine, bromine, methyl, ethyl,trifluoromethyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl ordifluoromethylsulfonyl;

R³ is hydrogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl or —OR⁷;

R⁴ is hydrogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-alkenyl orC₃-C₆-alkynyl, where the last 4 substituents mentioned may be partiallyor fully halogenated and/or carry one to three of the following groups:hydroxyl, mercapto, amino, cyano, —OR¹⁰, ═NOR¹⁰, —OCOR¹⁰, —CO₂R¹⁰,—COSR¹⁰, —CONR⁸R¹⁰, C₁-C₄-alkyliminooxy, C₁-C₄-alkylcarbonyl,C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, heterocyclyl, heterocyclyloxy,phenyl, benzyl, hetaryl, phenoxy, benzyloxy or hetaryloxy, where thelast eight radicals mentioned may in turn be partially or fullyhalogenated and/or carry one to three radicals from the following group:

nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkoxycarbonyl;

particularly preferably C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-alkenyl orC₃-C₆-alkynyl, where the last 4 substituents mentioned may be partiallyor fully halogenated and/or carry one to three of the following groups:hydroxyl, mercapto, amino, cyano, —OR¹⁰, ═NOR¹⁰, —OCOR¹⁰, —CO₂R¹⁰,—COSR¹⁰, —CONR⁸R¹⁰, C₁-C₄-alkyliminooxy, C₁-C₄-alkylcarbonyl,C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, heterocyclyl, heterocyclyloxy,phenyl, benzyl, hetaryl, phenoxy, benzyloxy or hetaryloxy, where thelast eight radicals mentioned may in turn be partially or fullyhalogenated and/or carry one to three radicals from the following group:

nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkoxycarbonyl;

X is oxygen or NH;

n is 0 or 2

R⁵ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₂-C₆-alkyl,C₃-C₆-alkenyl or C₃-C₆-alkynyl;

particularly preferably methyl, ethyl, trifluoromethyl, difluoromethyl,methoxyethyl, allyl or propargyl;

R⁷ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₂-C₆-alkyl,C₃-C₆-alkenyl or C₃-C₆-alkynyl;

particularly preferably methyl, ethyl, trifluoromethyl, difluoromethyl,methoxyethyl, allyl or propargyl;

R⁸ is hydrogen or C₁-C₆-alkyl;

R¹⁰ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl;

R¹¹, R¹², R¹⁴ and R¹⁶ are each hydrogen or C₁-C₄-alkyl;

particularly preferably hydrogen, methyl or ethyl;

R¹³ is hydrogen, C₁-C₄-alkyl, C₃-C₄-cycloalkyl, where the last twogroups may carry one to three of the following substituents: halogen,C₁-C₄-alkoxy or C₁-C₄-alkylthio; tetrahydropyran-2-yl,tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl,tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl,1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl,1,3-dithian-2-yl or 1,3-dithiolan-2-yl, where the last six groupsmentioned may in each case carry one to three C₁-C₄-alkyl radicals;

particularly preferably hydrogen, methyl, ethyl, cyclopropyl,di(methoxy)methyl, di(ethoxy)methyl, 2-ethylthiopropyl,tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl,tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl,tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl,5,5-dimethyl-1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl,1,3-dithiolan-2-yl, 5,5-dimethyl-1,3-dithian-2-yl or1-methylthiocyclopropyl;

R¹⁵ is hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxycarbonyl;

particularly preferably hydrogen, methyl or methoxycarbonyl.

It may also be advantageous for R¹³ and R¹⁶ to form a π-bond, thusforming a double bond system.

The CR¹³R¹⁴ unit may also be advantageously replaced by C═O.

Particular preference is given to compounds of the formula Ia ( I whereR¹ is attached in position 4 of the phenyl ring and R² is attached inposition 2 of the phenyl ring).

Very particular preference is given to the compounds of the formula Iain which R¹ to R³, Q and X are as defined above and

R⁴ is hydrogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-alkenyl orC₃-C₆-alkynyl, where the last 4 substituents may be partially or fullyhalogenated and/or carry one to three of the following groups: hydroxyl,mercapto, amino, cyano, —OR¹⁰, ═NOR¹⁰, —OCOR¹⁰, —CO₂R¹⁰, —COSR¹⁰,—CONR⁸R¹⁰, C₁-C₄-alkyliminooxy, C₁-C₄-alkylcarbonyl,C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, heterocyclyl, heterocyclyloxy,phenyl, benzyl, hetaryl, phenoxy, benzyloxy or hetaryloxy, where thelast eight radicals mentioned may in turn be partially or fullyhalogenated and/or carry one to three radicals from the following group:

nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkoxycarbonyl.

Most particular preference is given to the compounds Ia1 ( I whereR¹=Cl, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶=H, R¹ being attached in position 4of the phenyl ring and R² being attached in position 2 of the phenylring), in particular the compounds of Table 1.

TABLE 1 Ia1

No. R² R³ R⁴ X Ia1.001 Cl H CH₃ O Ia1.002 Cl H C₂H₅ O Ia1.003 Cl HCH₂—C≡CH O Ia1.004 Cl CH₃ CH₃ O Ia1.005 Cl CH₃ C₂H₅ O Ia1.006 Cl CH₃CH₂—C≡CH O Ia1.007 Cl C₂H₅ CH₃ O Ia1.008 Cl C₂H₅ C₂H₅ O Ia1.009 Cl C₂H₅CH₂—C≡CH O Ia1.010 Cl OCH₃ CH₃ O Ia1.011 Cl OCH₃ C₂H₅ O Ia1.012 Cl OCH₃CH₂—C≡CH O Ia1.013 Cl OC₂H₅ CH₃ O Ia1.014 Cl OC₂H₅ C₂H₅ O Ia1.015 ClOC₂H₅ CH₂—C≡CH O Ia1.016 Cl H CH₃ NH Ia1.017 Cl H C₂H₅ NH Ia1.018 Cl HCH₂—C≡CH NH Ia1.019 Cl CH₃ CH₃ NH Ia1.020 Cl CH₃ C₂H₅ NH Ia1.021 Cl CH₃CH₂—C≡CH NH Ia1.022 Cl C₂H₅ CH₃ NH Ia1.023 Cl C₂H₅ C₂H₅ NH Ia1.024 ClC₂H₅ CH₂—C≡CH NH Ia1.025 Cl OCH₃ CH₃ NH Ia1.026 Cl OCH₃ C₂H₅ NH Ia1.027Cl OCH₃ CH₂—C≡CH NH Ia1.028 Cl OC₂H₅ CH₃ NH Ia1.029 Cl OC₂H₅ C₂H₅ NHIa1.030 Cl OC₂H₅ CH₂—C≡CH NH Ia1.031 CH₃ H CH₃ O Ia1.032 CH₃ H C₂H₅ OIa1.033 CH₃ H CH₂—C≡CH O Ia1.034 CH₃ CH₃ CH₃ O Ia1.035 CH₃ CH₃ C₂H₅ OIa1.036 CH₃ CH₃ CH₂—C≡CH O Ia1.037 CH₃ C₂H₅ CH₃ O Ia1.038 CH₃ C₂H₅ C₂H₅O Ia1.039 CH₃ C₂H₅ CH₂—C≡CH O Ia1.040 CH₃ OCH₃ CH₃ O Ia1.041 CH₃ OCH₃C₂H₅ O Ia1.042 CH₃ OCH₃ CH₂—C≡CH O Ia1.043 CH₃ OC₂H₅ CH₃ O Ia1.044 CH₃OC₂H₅ C₂H₅ O Ia1.045 CH₃ OC₂H₅ CH₂—C≡CH O Ia1.046 CH₃ H CH₃ NH Ia1.047CH₃ H C₂H₅ NH Ia1.048 CH₃ H CH₂—C≡CH NH Ia1.049 CH₃ CH₃ CH₃ NH Ia1.050CH₃ CH₃ C₂H₅ NH Ia1.051 CH₃ CH₃ CH₂—C≡CH NH Ia1.052 CH₃ C₂H₅ CH₃ NHIa1.053 CH₃ C₂H₅ C₂H₅ NH Ia1.054 CH₃ C₂H₅ CH₂—C≡CH NH Ia1.055 CH₃ OCH₃CH₃ NH Ia1.056 CH₃ OCH₃ C₂H₅ NH Ia1.057 CH₃ OCH₃ CH₂—C≡CH NH Ia1.058 CH₃OC₂H₅ CH₃ NH Ia1.059 CH₃ OC₂H₅ C₂H₅ NH Ia1.060 CH₃ OC₂H₅ CH₂—C≡CH NHIa1.061 OCH₃ H CH₃ O Ia1.062 OCH₃ H C₂H₅ O Ia1.063 OCH₃ H CH₂—C≡CH OIa1.064 OCH₃ CH₃ CH₃ O Ia1.065 OCH₃ CH₃ C₂H₅ O Ia1.066 OCH₃ CH₃ CH₂—C≡CHO Ia1.067 OCH₃ C₂H₅ CH₃ O Ia1.068 OCH₃ C₂H₅ C₂H₅ O Ia1.069 OCH₃ C₂H₅CH₂—C≡CH O Ia1.070 OCH₃ OCH₃ CH₃ O Ia1.071 OCH₃ OCH₃ C₂H₅ O Ia1.072 OCH₃OCH₃ CH₂—C≡CH O Ia1.073 OCH₃ OC₂H₅ CH₃ O Ia1.074 OCH₃ OC₂H₅ C₂H₅ OIa1.075 OCH₃ OC₂H₅ CH₂—C≡CH O Ia1.076 OCH₃ H CH₃ NH Ia1.077 OCH₃ H C₂H₅NH Ia1.078 OCH₃ H CH₂—C≡CH NH Ia1.079 OCH₃ CH₃ CH₃ NH Ia1.080 OCH₃ CH₃C₂H₅ NH Ia1.081 OCH₃ CH₃ CH₂—C≡CH NH Ia1.082 OCH₃ C₂H₅ CH₃ NH Ia1.083OCH₃ C₂H₅ C₂H₅ NH Ia1.084 OCH₃ C₂H₅ CH₂—C≡CH NH Ia1.085 OCH₃ OCH₃ CH₃ NHIa1.086 OCH₃ OCH₃ C₂H₅ NH Ia1.087 OCH₃ OCH₃ CH₂—C≡CH NH Ia1.088 OCH₃OC₂H₅ CH₃ NH Ia1.089 OCH₃ OC₂H₅ C₂H₅ NH Ia1.090 OCH₃ OC₂H₅ CH₂—C≡CH NHIa1.091 CF₃ H CH₃ O Ia1.092 CF₃ H C₂H₅ O Ia1.093 CF₃ H CH₂—C≡CH OIa1.094 CF₃ CH₃ CH₃ O Ia1.095 CF₃ CH₃ C₂H₅ O Ia1.096 CF₃ CH₃ CH₂—C≡CH OIa1.097 CF₃ C₂H₅ CH₃ O Ia1.098 CF₃ C₂H₅ C₂H₅ O Ia1.099 CF₃ C₂H₅ CH₂—C≡CHO Ia1.100 CF₃ OCH₃ CH₃ O Ia1.101 CF₃ OCH₃ C₂H₅ O Ia1.102 CF₃ OCH₃CH₂—C≡CH O Ia1.103 CF₃ OC₂H₅ CH₃ O Ia1.104 CF₃ OC₂H₅ C₂H₅ O Ia1.105 CF₃OC₂H₅ CH₂—C≡CH O Ia1.106 CF₃ H CH₃ NH Ia1.107 CF₃ H C₂H₅ NH Ia1.108 CF₃H CH₂—C≡CH NH Ia1.109 CF₃ CH₃ CH₃ NH Ia1.110 CF₃ CH₃ C₂H₅ NH Ia1.111 CF₃CH₃ CH₂—C≡CH NH Ia1.112 CF₃ C₂H₅ CH₃ NH Ia1.113 CF₃ C₂H₅ C₂H₅ NH Ia1.114CF₃ C₂H₅ CH₂—C≡CH NH Ia1.115 CF₃ OCH₃ CH₃ NH Ia1.116 CF₃ OCH₃ C₂H₅ NHIa1.117 CF₃ OCH₃ CH₂—C≡CH NH Ia1.118 CF₃ OC₂H₅ CH₃ NH Ia1.119 CF₃ OC₂H₅C₂H₅ NH Ia1.120 CF₃ OC₂H₅ CH₂—C≡CH NH Ia1.121 SO₂CH₃ H CH₃ O Ia1.122SO₂CH₃ H C₂H₅ O Ia1.123 SO₂CH₃ H CH₂—C≡CH O Ia1.124 SO₂CH₃ CH₃ CH₃ OIa1.125 SO₂CH₃ CH₃ C₂H₅ O Ia1.126 SO₂CH₃ CH₃ CH₂—C≡CH O Ia1.127 SO₂CH₃C₂H₅ CH₃ O Ia1.128 SO₂CH₃ C₂H₅ C₂H₅ O Ia1.129 SO₂CH₃ C₂H₅ CH₂—C≡CH OIa1.130 SO₂CH₃ OCH₃ CH₃ O Ia1.131 SO₂CH₃ OCH₃ C₂H₅ O Ia1.132 SO₂CH₃ OCH₃CH₂—C≡CH O Ia1.133 SO₂CH₃ OC₂H₅ CH₃ O Ia1.134 SO₂CH₃ OC₂H₅ C₂H₅ OIa1.135 SO₂CH₃ OC₂H₅ CH₂—C≡CH O Ia1.136 SO₂CH₃ H CH₃ NH Ia1.137 SO₂CH₃ HC₂H₅ NH Ia1.138 SO₂CH₃ H CH₂—C≡CH NH Ia1.139 SO₂CH₃ CH₃ CH₃ NH Ia1.140SO₂CH₃ CH₃ C₂H₅ NH Ia1.141 SO₂CH₃ CH₃ CH₂—C≡CH NH Ia1.142 SO₂CH₃ C₂H₅CH₃ NH Ia1.143 SO₂CH₃ C₂H₅ C₂H₅ NH Ia1.144 SO₂CH₃ C₂H₅ CH₂—C≡CH NHIa1.145 SO₂CH₃ OCH₃ CH₃ NH Ia1.146 SO₂CH₃ OCH₃ C₂H₅ NH Ia1.147 SO₂CH₃OCH₃ CH₂—C≡CH NH Ia1.148 SO₂CH₃ OC₂H₅ CH₃ NH Ia1.149 SO_(2CH) ₃ OC₂H₅C₂H₅ NH Ia1.150 SO₂CH₃ OC₂H₅ CH₂—C≡CH NH Ia1.151 NO₂ H CH₃ O Ia1.152 NO₂H C₂H₅ O Ia1.153 NO₂ H CH₂—C≡CH O Ia1.154 NO₂ CH₃ CH₃ O Ia1.155 NO₂ CH₃C₂H₅ O Ia1.156 NO₂ CH₃ CH₂—C≡CH O Ia1.157 NO₂ C₂H₅ CH₃ O Ia1.158 NO₂C₂H₅ C₂H₅ O Ia1.159 NO₂ C₂H₅ CH₂—C≡CH O Ia1.160 NO₂ OCH₃ CH₃ O Ia1.161NO₂ OCH₃ C₂H₅ O Ia1.162 NO₂ OCH₃ CH₂—C≡CH O Ia1.163 NO₂ OC₂H₅ CH₃ OIa1.164 NO₂ OC₂H₅ C₂H₅ O Ia1.165 NO₂ OC₂H₅ CH₂—C≡CH O Ia1.166 NO₂ H CH₃NH Ia1.167 NO₂ H C₂H₅ NH Ia1.168 NO₂ H CH₂—C≡CH NH Ia1.169 NO₂ CH₃ CH₃NH Ia1.170 NO₂ CH₃ C₂H₅ NH Ia1.171 NO₂ CH₃ CH₂—C≡CH NH Ia1.172 NO₂ C₂H₅CH₃ NH Ia1.173 NO₂ C₂H₅ C₂H₅ NH Ia1.174 NO₂ C₂H₅ CH₂—C≡CH NH Ia1.175 NO₂OCH₃ CH₃ NH Ia1.176 NO₂ OCH₃ C₂H₅ NH Ia1.177 NO₂ OCH₃ CH₂—C≡CH NHIa1.178 NO₂ OC₂H₅ CH₃ NH Ia1.179 NO₂ OC₂H₅ C₂H₅ NH Ia1.180 NO₂ OC₂H₅CH₂—C≡CH NH

Furthermore, most particular preference is given to the following2-benzoylcyclohexane-1,3-diones of the formula I:

the compounds Ia2, in particular the compounds Ia2.001-Ia2.180, whichdiffer from the corresponding compounds Ia1.001-Ia1.180 in that R¹³ ismethyl:

 the compounds Ia3, in particular the compounds Ia3.001-Ia3.180, whichdiffer from the corresponding compounds Ia1.001-Ia1.180 in that R¹³ andR¹⁴ are each methyl:

 the compounds Ia4, in particular the compounds Ia4.001-Ia4.180, whichdiffer from the corresponding compounds Ia1.001-Ia1.180 in that R¹⁵ andR¹⁶ are each methyl:

 the compounds Ia5, in particular the compounds Ia5.001-Ia5.180, whichdiffer from the corresponding compounds Ia1.001-Ia1.180 in that theCR¹³R¹⁴ unit is replaced by C═O:

 the compounds Ia6, in particular the compounds Ia6.001-Ia6.180, whichdiffer from the corresponding compounds Ia1.001-Ia1.180 in that R¹¹, R¹⁵and R¹⁶ are each methyl and the CR¹³R¹⁴ unit is replaced by C═O:

 the compounds Ia7, in particular the compounds Ia7.001-Ia7.180, whichdiffer from the corresponding compounds Ia1.001-Ia1.180 in that R¹¹,R¹², R¹⁵ and R¹⁶ are each methyl and the CR¹³R¹⁴ unit is replaced byC═O:

 the compounds Ia8, in particular the compounds Ia8.001-Ia8.180, whichdiffer from the corresponding compounds Ia1.001-Ia1.180 in that R¹ isnitro:

 the compounds Ia9, in particular the compounds Ia9.001-Ia9.180, whichdiffer from the corresponding compounds Ia1.001-Ia1.180 in that R¹ isnitro and R¹³ is methyl:

 the compounds Ia10, in particular the compounds Ia10.001-Ia10.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is nitro and R¹³ and R¹⁴ are each methyl:

 the compounds Ia11, in particular the compounds Ia11.001-Ia11.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is nitro and R¹⁵ and R¹⁶ are each methyl:

 the compounds Ia12, in particular the compounds Ia12.001-Ia12.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is nitro and the CR¹³R¹⁴ unit is replaced by C═O:

 the compounds Ia13, in particular the compounds Ia13.001-Ia13.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is nitro, R¹¹, R¹⁵ and R¹⁶ are each methyl and the CR¹³R¹⁴ unit isreplaced by C═O:

 the compounds Ia14, in particular the compounds Ia14.001-Ia14.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is nitro, R¹¹, R¹², R¹⁵ and R¹⁶ are each methyl and the CR¹³R¹⁴ unit isreplaced by C═O:

 the compounds Ia15, in particular the compounds Ia15.001-Ia15.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is methylsulfonyl:

 the compounds Ia16, in particular the compounds Ia16.001-Ia16.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is methylsulfonyl and R¹³ is methyl:

 the compounds Ia17, in particular the compounds Ia17.001-Ia17.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is methylsulfonyl and R¹³ and R¹⁴ are each methyl:

 the compounds Ia18, in particular the compounds Ia18.001-Ia18.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is methylsulfonyl and R¹⁵ and R¹⁶ are each methyl:

 the compounds Ia19, in particular the compounds Ia19.001-Ia19.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is methylsulfonyl and the CR¹³R¹⁴ unit is replaced by C═O:

 the compounds Ia20, in particular the compounds Ia20.001-Ia20.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is methylsulfonyl, R¹¹, R¹⁵ and R¹⁶ are each methyl and the CR¹³R¹⁴ unitis replaced by C═O:

 the compounds Ia21, in particular the compounds Ia21.001-Ia21.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is methylsulfonyl, R¹¹ R¹² R¹⁵ and R¹⁶ are each methyl and the CR¹³R¹⁴unit is replaced by C═O:

 the compounds Ia22, in particular the compounds Ia22.001-Ia22.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is trifluoromethyl:

 the compounds Ia23, in particular the compounds Ia23.001-Ia23.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is trifluoromethyl and R¹³ is methyl:

 the compounds Ia24, in particular the compounds Ia24.001-Ia24.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is trifluoromethyl and R¹³ and R¹⁴ are each methyl:

 the compounds Ia25, in particular the compounds Ia25.001-Ia25.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is trifluoromethyl and R¹⁵ and R¹⁶ are each methyl:

 the compounds Ia26, in particular the compounds Ia26.001-Ia26.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is trifluoromethyl and the CR¹³R¹⁴ unit is replaced by C═O:

 the compounds Ia27, in particular the compounds Ia27.001-Ia27.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is trifluoromethyl, R¹¹, R¹⁵ and R¹⁶ are each methyl and the CR¹³R¹⁴unit is replaced by C═O:

 the compounds Ia28, in particular the compounds Ia28.001-Ia28.180,which differ from the corresponding compounds Ia1.001-Ia1.180 in that R¹is trifluoromethyl, R¹¹, R¹², R¹⁵ and R¹⁶ are each methyl and theCR¹³R¹⁴ unit is replaced by C═O:

Extraordinary preference is given to the compounds of the formula Ia′ Iwhere R¹ is attached in position 4 of the phenyl ring and R² is attachedin position 2 of the phenyl ring)

where

R¹ is halogen or C₁-C₄-alkylsulfonyl;

R² is halogen or C₁-C₄-alkyl, in particular halogen;

R³ is hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy, in particular hydrogen orC₁-C₄-alkoxy;

R⁴ is C₁-C₆-alkyl, C₃-C₆-alkynyl, where these two substituents may bepartially or fully halogenated and/or may carry one to three of thefollowing groups: phenyl or hetaryl, where these groups may in turn bepartially or fully halogenated;

X is oxygen;

R¹¹, R¹² ₁ R¹³, R¹⁴, R¹⁵, R¹⁶ are each hydrogen or C₁-C₄-alkyl.

The 2-benzoylcyclohexane-1,3-diones of the formula I can be obtained ina variety of ways, for example by the following process:

Reaction of cyclohexanediones of the formula II with an activatedcarboxylic acid IIIα or a carboxylic acid IIIβ which is preferablyactivated in situ, to give the acylation product IV, and activatedsubsequent rearrangement.

L is a nucleophilically replaceable leaving group, such as halogen, forexample bromine or chlorine, hetaryl, for example imidazolyl or pyridyl,carboxylate, for example acetate or trifluoroacetate, etc.

The activated carboxylic acid can be employed directly, as in the caseof the acyl halides, or be generated in situ, for example by usingdicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic acidesters, 2 pyridine disulfite [sic]/triphenylphosphine,carbonyldiimidazole, etc.

If appropriate, it may be advantageous to carry out the acylationreaction in the presence of a base. The reactants and the auxiliary baseare advantageously employed in equimolar amounts. A slight excess of theauxiliary base, for example 1.2 to 1.5 molar equivalents based on II,may be advantageous in certain instances.

Suitable auxiliary bases are tertiary alkylamines, pyridine or alkalimetal carbonates. Suitable solvents are, for example, chlorinatedhydrocarbons, such as methylene chloride and 1,2-dichloroethane,aromatic hydrocarbons, such as toluene, xylene or chlorobenzene, ethers,such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran anddioxane, polar aprotic solvents, such as acetonitrile, dimethylformamideand dimethyl sulfoxide, or esters such as ethyl acetate, or mixtures ofthese.

If acyl halides are used as activated carboxylic acid component, it maybe advantageous to cool the reaction mixture to 0-10° C. when addingthis reaction partner. Subsequently, the mixture is stirred at 20-100°C., preferably at 25-50° C., until the reaction has ended. Work-up iscarried out in a conventional manner, for example by pouring thereaction mixture into water and extracting the product of value.Suitable solvents for this purpose are in particular methylene chloride,diethyl ether and ethyl acetate. After drying off the organic phase andremoval of the solvent, crude enol ester of the formula IV is preferablypurified by chromatography. However, it is also possible to use thecrude enol ester of the formula IV without further purification for therearrangement.

The rearrangement of the enol esters of the formula IV to the compoundsof the formula I is advantageously carried out at temperatures from 20to 40° C. in a solvent and in the presence of an auxiliary base and, ifappropriate, with the aid of a cyano compound as catalyst.

Suitable solvents are, for example, acetonitrile, methylene chloride,1,2-dichloroethane, ethyl acetate, toluene or mixtures of these. Thepreferred solvent is acetonitrile.

Suitable auxiliary bases are tertiary amines such as triethylamine orpyridine, or alkali metal carbonates, such as sodium carbonate andpotassium carbonate, which are preferably employed in equimolar amountsor in up to four-fold excess, based on the enol ester. Preference isgiven to using triethylamine, preferably in twice the equimolar amount,based on the enol ester.

Suitable “rearrangement catalysts” are inorganic cyanides, such assodium cyanide and potassium cyanide, and organic cyano compounds, suchas acetone cyanohydrin and trimethylsilyl cyanide. They areconventionally used in an amount of from 1 to 50 mol percent, based onthe enol ester. Preference is given to using acetone cyanohydrin ortrimethylsilyl cyanide, for example in an amount of from 5 to 15,preferably 10, mol percent, based on the enol ester.

Workup can be carried out in a manner known per se. For example, thereaction mixture is acidified with dilute mineral acid, such as, forexample 5% strength hydrochloric acid or sulfuric acid, and extractedwith an organic solvent, for example methylene chloride or ethylacetate. The organic extract may be extracted with 5-10% strength alkalimetal carbonate solution, for example sodium carbonate or potassiumcarbonate solution. The aqueous phase is acidified and the resultingprecipitate is filtered off with suction and/or extracted with methylenechloride or ethyl acetate, dried and concentrated.

(Examples of the preparation of enol esters from cyclohexane-1,3-dionesand of the cyanide-catalyzed rearrangement of the enol esters are given,for example, in EP-A 186 118, U.S. Pat. No. 4,780,127).

The cyclohexane-1,3-diones of the formula II used as starting materialsare known or can be prepared by known processes (for example EP-A 71707, EP-A 142 741, EP-A 243 313, U.S. Pat. No. 4,249,937; WO 92/13821).

The benzoic acid derivatives of the formula III are novel,

where:

R¹, R² are each hydrogen, nitro, halogen, cyano, thiocyanato,C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl,C₂-C₆-alkynyl, —OR⁵, —OCOR⁶, —OSO₂R⁶, —SH, —S(O)_(n)R⁷, —SO₂OR⁵,—SO₂NR⁵R⁸, —NR⁸SO₂R⁶ or —NR⁸COR⁶;

R³ is hydrogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl, —OR⁷, —SR⁷ or—NR⁷R¹⁰;

R⁴ is hydrogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-alkenyl,C₄-C₆-cycloalkenyl, C₃-C₆-alkynyl, —COR⁹, —CO₂R⁹, —COSR⁹ or —CONR⁸R⁹,where the alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicalsmentioned and R⁹ of the radicals —COR⁹, —CO₂R⁹, —COSR⁹ and —CONR⁸R⁹ maybe partially or fully halogenated and/or carry one to three of thefollowing groups:

hydroxyl, mercapto, amino, cyano, R¹⁰, —OR¹⁰, —SR¹⁰, —NR⁸R¹⁰,═NOR¹⁰,—OCOR¹⁰, —SCOR¹⁰, —NR⁸COR¹⁰, —CO₂R¹⁰, —COSR¹⁰, —CONR⁸R¹⁰,C₁-C₄-alkyliminooxy, C₁-C₄-alkoxyamino, C₁-C₄-alkylcarbonyl,C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, C₁-C₄-alkylsulfonyl, heterocyclyl,heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy andhetaryloxy, where the last eight radicals mentioned may in turn besubstituted;

X is oxygen or NR⁸;

n is 0, 1 or 2;

R⁵ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₂-C₆-alkyl,C₃-C₆-alkenyl or C₃-C₆-alkynyl;

R⁶ is C₁-C₆-alkyl or C₁-C₆-haloalkyl;

R⁷ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₄-C₆-alkoxy-C₂-C₆-alkyl,C₃-C₆-alkenyl or C₃-C₆-alkynyl;

R⁸ is hydrogen or C₁-C₆-alkyl;

R⁹ is C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, phenyl or benzyl;

R¹⁰ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl;

R¹⁷ is hydroxyl or a radical that can be removed by hydrolysis.

Examples of radicals that can be removed by hydrolysis are alkoxy,phenoxy, alkylthio and phenylthio radicals with or without substitution,halides, hetaryl radicals which are attached via nitrogen, amino andimino radicals with or without substitution, etc.

Preference is given to benzoyl halides IIIα, where L=halogen III whereR¹⁷=halogen),

where the variables R¹ to R⁴ and X are each as defined under formula IIIand

L is halogen, in particular chloride or bromide.

Preference is also given to the benzoic acids of the formula IIIβ IIIwhere R¹⁷=hydroxyl),

where the variables R¹ to R⁴ and X are each as defined under formulaIII.

Preference is also given to the benzoic acid esters of the formula IIIγ( III where M=C₁-C₆-alkoxy)

where the variables R¹ to R⁴ and X are each as defined under formula IIIand

M is C₁-C₆-alkoxy.

With regard to the preferred compounds of the formula III, the remarksmade under the compounds I apply to the radicals R¹ to R⁴ and X.

The compounds of the formula IIIα (where L=halogen) can be prepared in asimilar manner to literature methods (cf. L. G. Fieser, M. Fieser“Reagents for Organic Synthesis”, Vol. I, p. 767-769 (1967)) by reactingbenzoic acids of the formula IIIβ with halogenating reagents such asthionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene,oxalyl chloride or oxalyl bromide.

The benzoic acids of the formula IIIβ can be obtained in a similarmanner to literature methods, inter alia by hydrolysis of the benzoicacid esters of the formula IIIγ (where M=C₁-C₆-alkoxy).

The benzoic acid esters of the formula IIIγ are obtainable in a varietyof ways, for example by the following processes:

Isophthalic acid derivatives of the formula VI can be obtained byoxidation of aldehydes of the formula V in a manner known per se (J.March, “Advanced Organic Chemistry”, 3rd Edition, p. 629 ff,Wiley-Interscience Publication, 1985).

In a similar manner to literature methods, the compounds of the formulaVI can initially be converted into the corresponding activatedcarboxylic acids VII where L¹ is a nucleophilically displaceable leavinggroup such as halogen, for example bromine or chlorine, hetaryl, forexample imidazolyl or pyridyl, carboxylate, for example acetate ortrifluoracetate etc., and then into the corresponding hydroxamic acid orcarbohydrazide derivatives of the formula VIII (Australian J. Chem. 22,(1969), 1731-1735; ibid 22 (1969), 161-173; J. Org. Chem. 27 (1974),1341-1349).

Alkylation of compounds of the formula VIII leads to compounds of theformula IIIγ (where R³=OR⁷) in a manner known per se (EP-A 463 989;Synthesis (1983), 220-222; U.S. Pat. No. 4,931,088; J. Org. Chem. 31(1971), 284-294; J. Chem. Soc. Perk. II (1977), 1080-1084).

Compounds of the formula IIIγ are obtained in a manner known per se byreacting aldehydes/ketones of the formula IX with “alkoxamines oralkylhydrazines”. In a similar manner to processes known from theliterature, it is possible to react aldehydes/ketones of the formula IXwith hydroxylamine or hydrazine and to alkylate them subsequently (J.March, “Advanced Organic Chemistry”, 3rd Edition, p. 359, p. 805-806,Wiley-Interscience Publication, 1985).

It is possible to convert nitriles of the formula X in a manner knownper se by alcoholysis (R⁷OH) into imino esters which can be reacted in afurther step with hydroxylamines or hydrazines to give compounds of theformula IIIγ (J. March, “Advanced Organic Chemistry”, 3rd Edition, p.792-793, Wiley-Interscience Publication, 1985; U.S. Pat. No. 4,965,390).

In a similar manner to processes known from the literature, nitriles ofthe formula X can be prepared from the corresponding aldehydes V (J.March, “Advanced Organic Chemistry”, 3rd Edition, p. 806-807,Wiley-Interscience Publication, 1985). It is also possible to obtainnitrites of the formula X from anilines of the formula XI by employingthe Sandmeyer reaction or from aryl halides of the formula XII by theRosemund/von Braun reaction using metal cyanides, in particular CuCN (J.March, “Advanced Organic Chemistry”, 3rd Edition, p. 594, p. 648,Wiley-Interscience Publication, 1985).

In a similar manner to processes known from the literature, thealdehydes of the formula V can be prepared from the correspondingtoluenes of the formula XIII by conversion into the ω-halotoluene XIVand subsequent oxidation (cf. Synth. Commun. 22 (1992) 1967-1971).

PREPARATION EXAMPLES

2-(2,4-Dichloro-3-propargyloxyiminomethylbenzoyl)-5,5-dimethyl-1,3-cyclohexanedione(compound 2.12)

1.20 g (0.0086 mol) of dimedone and 1.80 g (0.0086 mol) ofdicyclohexylcarbodiimide were added to a solution of 2.50 g (0.0092 mol)of 2,4-dichloro-3-propargyloxyiminomethyl-benzoic acid in 120 ml of dryacetonitrile. After stirring for 12 hours at room temperature, themixture was filtered through silica gel (eluent:toluene), the solventwas then removed and the residue was taken up in 100 ml of dryacetonitrile and admixed with 0.40 g (0.0047 mol) of acetone cyanohydrinand 3.10 g (0.031 mol) of triethylamine. The reaction mixture was thenstirred for 3 hours at room temperature and subsequently added to amixture of 200 ml of water and 100 ml of 5% strength potassium carbonatesolution. The aqueous phase was washed three times with ethyl acetate,then adjusted to pH=2 using 10% strength hydrochloric acid and extractedthree times with ethyl acetate. The combined organic phases were washedwith water until neutral, dried and concentrated. 0.7 g of2-(2,4-dichloro-3-propargyloxyimino-methylbenzoyl)-5,5-dimethyl-cyclohexanedionewas obtained.

(¹H-NMR (CDCl₃, δ in ppm): 1.13 (6H); 2.32 (2H); 2.52 (1H); 2.66 (2H);4.81 (2H); 7.12 (1H); 7.43 (1H); 8.31 (1H); 16.48 (1H).)2-(2-Chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoyl)-5,5-dimethyl-1,3-cyclohexanedione(compound 2.07)

1.26 g (0.009 mol) of dimedone and 1.90 g (0.009 mol) ofdicyclohexylcarbodiimide were added to a solution of 2.95 g (0.009 mol)of 2-chloro-3-ethoxyiminomethyl-4-methylsulfonyl-benzoic acid in 130 mlof anhydrous acetonitrile. After stirring for 12 hours at roomtemperature, 0.42 g (0.005 mol) of acetone cyanohydrin and 3.27 g (0.032mol) of triethylamine in 10 ml of absolute acetonitrile were addeddropwise. The reaction mixture was then stirred for a further 2 hours atroom temperature. With stirring, the reaction mixture was poured into200 ml of water, the precipitate was filtered off with suction and thefiltrate was added to 100 ml of 5% strength potassium carbonatesolution. The aqueous phase was washed with ethyl acetate, the pH wasadjusted to 2 using 10% strength hydrochloric acid and the mixture wasextracted with ethyl acetate. The combined organic phases were washedwith water until neutral, dried and concentrated under reduced pressure.This gave 2.52 g of crude product which was recrystallized from toluene.(mp.: 156-157° C.)

2-[2,4-Dichloro-3-(1′-methoxyimino-1′-(methoxy)methyl)benzoyl]-1,3-cyclohexanedione(compound 2.10)

1.125 g (0.0038 mol) of2,4-dichloro-3(1′-methoxyimino-1′-(methoxy)methyl)benzoyl chloride wereadded to a solution of 0.46 g (0.0045 mol) of triethylamine and 0.5 g(0.0045 mol) of 1,3-cyclohexanedione in 50 ml of methylene chloride. Thereaction solution was stirred at room temperature for 2 hours and thesolvent was then removed under reduced pressure. The residue waspurified by silica gel chromatography (eluent:toluene/ethylacetate=1/1). The enol ester obtained in this manner was taken up in 50ml of acetonitrile and admixed with 0.80 g (0.008 mol) of triethylamineand 0.15 g (0.0015 mol) of trimethylsilyl cyanide. After stirring for 12hours at room temperature, the solvent was removed and the residue wastaken up in methylene chloride. The organic phase was washed with dilutephosphoric acid, dried and concentrated. This gave 0.90 g of2-[2,4-dichloro-3-(1′-methoxyimino-1′-(methoxy)methyl)benzoyl]-1,3-cyclohexanedionewhich was digested with diethyl ether. (mp.: 180-182° C.)

In addition to the above-described benzoyl derivatives of the formula I,further compounds prepared or preparable in a similar manner are listedin Table 2 below:

TABLE 2 Ia

Physical data No. X R¹ R² R³ R⁴ R¹³ R¹⁴ R¹⁵ R¹⁶ mp. [° C.]; ¹H NMR [ppm]2.01 O Cl Cl H CH₃ H H H H 177-185 2.02 O Cl Cl H CH₃ CH₃ H H H 106-1082.03 O Cl Cl H CH₃ CH₃ CH₃ H H 158-160 2.04 O Cl Cl H CH₃ H H CH₃ CH₃1.15(6H); 1.84(2H); 2.78(2H); 3.97(3H); 7.08(1H); 7.39(1H); 8.22(1H);16.81(1H) 2.05 O Cl Cl OC₂H₅ n-C₃H₇ H H H H 140-142 2.06 O Cl Cl H C₂H₅CH₃ H H H 114-115 2.07 O SO₂CH₃ Cl H C₂H₅ CH₃ CH₃ H H 156-157 2.08 O ClCl H C₂H₅ CH₃ CH₃ H H 1.15(6H); 1.33(3H); 2.32(2H); 2.64(2H); 4.23(2H);7.12(1H); 7.43(1H); 8.23(1H); 16.95(1H) 2.09 O Cl Cl OCH₃ CH₂-4-Cl—C₆H₄CH₃ CH₃ H H 138-142 2.10 O Cl Cl OCH₃ CH₃ H H H H 180-182 2.20(2H);2.55(1H); 2.64(2H); 3.03(2H); 2.11 O Cl Cl H CH₂C≡CH H H H H 4.85(2H);7.44(1H); 8.19(1H); 8.52(1H); 16.92(1H) 1.13(6H); 2.32(2H); 2.52(1H);2.66(2H); 2.12 O Cl Cl H CH₂C≡CH CH₃ CH₃ H H 4.81(2H); 7.12(1H);7.43(1H); 8.31(1H); 16.48(1H) 2.13 O Cl Cl OCH₃ n-C₃H₇ H H H H 78-802.14 O Cl Cl OCH₃ CH₂-4-Cl—C₆H₄ H H H H 157-158 2.15 O SO₂CH₃ Cl H CH₃ HH H H 55-60 2.16 O SO₂CH₃ Cl H C₂H₅ CH₃ CH₃ H H 95-100 2.17 O SO₂CH₃ ClCH₃ CH₃ CH₃ H H H 2.18 O SO₂CH₃ Cl CH₃ CH₃ CH₃ CH₃ H H 2.19 O SO₂CH₃ ClCH₃ CH₃ H H H H 2.20 O SO₂CH₃ CH₃ CH₃ CH₃ H H H H 145-151 2.21 O SO₂CH₃CH₃ CH₃ CH₃ CH₃ H H H 2.22 O SO₂CH₃ CH₃ CH₃ CH₃ CH₃ CH₃ H H 190-192

The syntheses of some starting materials are listed below:

2-Chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoic acid (compound3.04)

Step a) 2-Chloro-3-methyl-4-methylthioacetophenone

At 15-20° C., a solution of 157 g (2 mol) of acetyl chloride in 420 mlof 1,2-dichloroethane was added dropwise to a suspension of 286 g (2.14mol) of aluminum trichloride in 420 ml of 1,2-dichloroethane. A solutionof 346 g (2 mol) of 2-chloro-6-methylthiotoluene in 1 l of1,2-dichloroethane was then added dropwise. After stirring for 12 hours,the reaction mixture was poured into a mixture of 3 l of ice and 1 l ofconcentrated HCl. The mixture was extracted with methylene chloride andthe organic phase was washed with water, dried with sodium sulfate andconcentrated. The residue was distilled under reduced pressure. 256 g(60% of theory) of 2-chloro-3-methyl-4-methylthioacetophenone wereobtained.

(mp.: 46° C.)

Step b) 2-Chloro-3-methyl-4-methylsulfonylacetophenone 163.0 g (0.76mol) of 2-chloro-3-methyl-4-methylthioacetophenone were dissolved in 1.51 of glacial acetic acid and mixed with 18.6 g of sodium tungstate. Withcooling, 173.3 g of a 30% strength hydrogen peroxide solution were addeddropwise. Stirring was continued for a further 2 days and the mixturewas then diluted with water. The precipitated solid was filtered offwith suction, washed with water and dried. 164.0 g (88% of theory) of2-chloro-3-methyl-4-methylsulfonylacetophenone were obtained.

(mp.: 110-111° C.)

Step c) 2-Chloro-3-methyl-4-methylsulfonylbenzoic acid 82 g (0.33 mol)of 2-chloro-3-methyl-4-methylsulfonylacetophenone were dissolved in 700ml of dioxane and treated with 1 l of a 12.5% strength sodiumhypochlorite solution at room temperature. The mixture was then stirredfor 1 hour at 80° C. After cooling, two phases formed, the lower one ofwhich was diluted with water and acidified slightly. The precipitatedsolid was filtered off with suction, washed with water and dried. 60 g(73% of theory) of 2-chloro-3-methyl-4-methylsulfonylbenzoic acid wereobtained.

(mp.: 230-231° C.)

Step d) Methyl 2-chloro-3-methyl-4-methylsulfonylbenzoate

100 g (0.4 mol) of 2-chloro-3-methyl-4-methyl-sulfonyl-benzoic acid weredissolved in 1 l of methanol and treated with hydrogen chloride gas for5 hours at reflux temperature. The mixture was then concentrated. Thisgave 88.5 g (84% of theory) of methyl2-chloro-3-methyl-4-methylsulfonylbenzoate.

(mp.: 107-108° C.)

Step e) Methyl 3-bromomethyl-2-chloro-4-methylsulfonylbenzoate

82 g (0.31 mol) of methyl 2-chloro-3-methyl-4-methylsulfonylbenzoatewere dissolved in 2 l of carbon tetrachloride and, with exposure tolight, admixed a little at a time with 56 g (0.31 mol) ofN-bromosuccinimide. The reaction mixture was filtered, the filtrate wasconcentrated and the residue was taken up in 200 ml of methyl tert-butylether. The solution was admixed with petroleum ether and theprecipitated solid was filtered off with suction and dried. 74.5 g (70%of theory) of methyl 3-bromomethyl-2-chloro-4-methylsulfonylbenzoatewere obtained.

(mp.: 74-75° C.)

Step f) Methyl 2-chloro-3-formyl-4-methylsulfonylbenzoate

A solution of 41.0 g (0.12 mol) of methyl3-bromomethyl-2-chloro-4-methylsulfonylbenzoate in 250 ml ofacetonitrile was admixed with 42.1 g (0.36 mol) of N-methylmorpholineN-oxide. The reaction mixture was stirred for 12 hours at roomtemperature and then concentrated, and the residue was taken up in ethylacetate. The solution was extracted with water, dried with sodiumsulfate and concentrated. 31.2 g (94% of theory) of methyl2-chloro-3-formyl-4-methylsulfonylbenzoate were obtained.

(mp.: 98-105° C.)

Step g) 2-Chloro-3-formyl-4-methylsulfonylbenzoic acid

At reflux temperature, a solution of 5.00 g (0.018 mol) of methyl2-chloro-3-formyl-4-methylsulfonylbenzoate was added dropwise to asolution of 9.60 g (0.072 mol) of lithium iodide and 70 ml of drypyridine. After stirring under reflux for 2 hours, the reaction mixturewas cooled and the solvent was removed under reduced pressure. Theresidue was then taken up in water and adjusted to pH 1-2 with dilutehydrochloric acid. The aqueous phase was extracted with ethyl acetateand the combined organic phases were washed with water until neutral,dried and concentrated. 4.00 g of2-chloro-3-formyl-4-methylsulfonylbenzoic acid (85% yield) wereobtained.

(¹H NMR (d⁶-DMSO, δ in ppm): 3.41 (s, 3H); 8.05 (d, 1H); 8.11 (d, 1H);10.49 (s, 1H); 14.21 (s, br., 1H).)

Step h) 2-Chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoic acid

1.63 g (0.017 mol) of O-ethylhydroxylamine hydrochloride and 1.15 g(0.0085 mol) of finely powdered potassium carbonate were stirred for 1hour in 60 ml of dry methanol. 4.00 g (0.015 mol) of2-chloro-3-formyl-4-methylsulfonylbenzoic acid in 40 ml of methanol werethen added. After stirring for 12 hours at room temperature, the solventwas removed, the residue was taken up in ethyl acetate and the organicphase was washed four times with water. After drying and removal of thesolvent by distillation, 3.60 g of2-chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoic acid (78% yield)were obtained.

(mp.: 155-160° C.)

alternatively:

Step g′) Methyl 2-chloro-3-ethoxyiminomethyl-4-methylsulfonyl-benzoate(compound 3.01)

1.90 g (0.0195 mol) of O-ethylhydroxylamine hydrochloride and 1.35 g(0.0097 mol) of finely powdered potassium carbonate were stirred for 1hour at room temperature in 60 ml of dry methanol, and 4.90 g (0.0177mol) of methyl 2-chloro-3-formyl-4-methylsulfonylbenzoate were thenadded. After stirring for 8 hours at room temperature, the solvent wasremoved, the residue was taken up in ethyl acetate and the organic phasewas washed with water until neutral, dried and concentrated underreduced pressure. 5.00 g of methyl2-chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoate were obtained.(Yield 88%).

(¹H NMR (CDCl₃, δ in ppm): 1.34 (t, 3H); 3.29 (s, 3H); 3.98 (s, 3H);4.26 (q, 2H); 7.91 (d, 1H); 8.10 (d, 1H); 8.38 (s, 1H).)

Step h′) 2-Chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoic acid

A solution of 4.37 g (0.0137 mol) of methyl2-chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoate was slowly addeddropwise to 7.29 g (0.055 mol) of lithium iodide in 50 ml of drypyridine. After stirring for 2 hours at reflux, the reaction mixture wascooled and the solvent was removed under reduced pressure. The residuewas taken up in water and adjusted to pH=1-2 with dilute hydrochloricacid. The aqueous phase was extracted with ethyl acetate and thecombined organic phases were washed with water, dried and concentratedunder reduced pressure. 3.70 g of2-chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoic acid were obtained.(Yield 89%).

(mp.: 155-160° C.)

Methyl 2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate

Step a) Methyl 2-chloro-3-hydroxycarbonyl-4-methylsulfonylbenzoate

At 5° C., 13.8 g (0.11 mol) of sodium hydrogen phosphate monohydrate in170 ml of water, 49.3 g (0.43 mol) of 30% strength hydrogen peroxidesolution and 66.2 g (0.59 mol) of 80% strength aqueous sodium chloritesolution were added in succession to a solution of 115.3 g (0.42 mol) ofmethyl 2-chloro-3-formyl-4-methylsulfonylbenzoate and 2000 ml ofacetonitrile. The reaction solution was then stirred for 1 hour at 5° C.and for 12 hours at room temperature. The pH was then adjusted to 1using 10% strength hydrochloric acid, and 1500 ml of aqueous 40%strength sodium hydrogen sulfite solution were added. After stirring for1 hour at room temperature, the aqueous phase was extracted three timeswith ethyl acetate. The combined organic phases were washed with sodiumhydrogen sulfite solution and dried. Removal of the solvent bydistillation gave 102.0 g of methyl2-chloro-3-hydroxycarbonyl-4-methylsulfonylbenzoate.

(¹H NMR (d⁶-DMSO, δ in ppm): 3.34 (s, 3H); 3.93 (s, 3H); 8.08 (s, 2H);14.50 (s, br., 1H).)

Step b) Methyl 2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate

2 drops of dimethylformamide and 11.9 g (0.1 mol) of thionyl chloridewere added to a solution of 6.0 g (0.021 mol) of methyl2-chloro-3-hydroxycarbonyl-4-methylsulfonylbenzoate and 50 ml of drytoluene. The solution was heated under reflux for 4 hours. After removalof the solvent under reduced pressure, 6.2 g of methyl2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate were obtained.

(¹H NMR (CDCl₃; δ in ppm): 3.21 (s, 3H); 4.02 (s, 3H); 8.02 (d, 1H);8.07 (d, 1H).)

2,4-Dichloro-3-(1′-methoxyimino-1′-(methoxy)methyl)benzoyl chloride(compound 3.14)

Step a) 2,4-Dichloro-3-methylacetophenone

At 100° C., 235.0 g (3.0 mol) of acetyl chloride were added dropwisewith stirring over a period of 2 hours to a solution of 502.0 g (3.12mol) of 2,6-dichlorotoluene and 408.0 g (3.06 mol) of aluminumtrichloride. After 2 hours of stirring at 100-105° C., the reactionmixture was cooled and poured into 3 1 of ice and 1 1 of water. Theprecipitated solid was filtered off with suction and washed with 800 mlof water until neutral. Drying at 40° C. yielded 500.0 g of crude2,4-dichloro-3-methylacetophenone which was subsequently distilled usinghigh vacuum.

(bp.: 121-128° C. (4 mbar))

Step b) 2,4-Dichloro-3-methylbenzoic acid

At 0-10° C., first 655.2 g (4.1 mol) of bromine and then 203.0 g (1.0mol) of 2,4-dichloro-3-methyl-acetophenone in 1300 ml of 1,4-dioxanewere added dropwise to a solution of 520.0 g (13 mol) of sodiumhydroxide in 2600 ml of water. After stirring for 12 hours, the organicphase was separated off, the aqueous phase was admixed with a 30%strength aqueous sodium pyrosulfite solution and the pH was adjusted to1 using hydrochloric acid. The precipitated solid was filtered off withsuction, washed with water and dried at 60° C. under reduced pressure.197.0 g of 2,4-dichloro-3-methylbenzoic acid were obtained.

(mp.: 173-175° C.)

Step c) Methyl 2,4-dichloro-3-methylbenzoate

60 ml of concentrated sulfuric acid were added dropwise to a solution of424.0 g (2 mol) of 2,4-dichloro-3-methylbenzoic acid and 1500 ml ofmethanol. After heating for 5 hours under reflux, the reaction mixturewas cooled, concentrated under reduced pressure and then taken up in1000 ml of methylene chloride. The organic phase was washed with water,then with 5% strength of sodium hydrogen carbonate solution and thenagain with water, dried and concentrated under reduced pressure. 401.0 gof methyl 2,4-dichloro-3-methylbenzoate were obtained.

(bp: 103-107° C. (1-1.5 mbar))

Step d) Methyl 3-bromomethyl-2,4-dichlorobenzoate

1.0 g of azobisisobutyronitrile was added to a solution of 84.0 g (0.38mol) of methyl 2,4-dichloro-3-methylbenzoate and 67.6 g (0.38 mol) ofN-bromosuccinimide in 380 ml of carbon tetrachloride. After heating for3.5 hours under reflux, the reaction mixture was cooled and theresulting precipitate was filtered off with suction. The filtrate wasconcentrated under reduced pressure and the resulting residue wastriturated with methyl tert-butyl ether. 108.0 g of methyl3-bromomethyl-2,4-dichlorobenzoate were obtained.

(mp.: 51-54° C.)

Step e) Methyl 2,4-dichloro-3-formylbenzoate

At reflux, 696.2 g (2.97 mol) of aqueous 50% strength N-methylmorpholineN-oxide solution were added to a solution of 312.0 g (0.99 mol) ofmethyl 3-bromomethyl-2,4-dichlorobenzoate in 2 l of acetonitrile. Afterstirring for 48 hours at room temperature, the reaction solution wasstirred into 6 l of water. The precipitate was filtered off withsuction, washed with water and dried under reduced pressure. 141.3 g ofmethyl 2,4-dichloro-3-formylbenzoate were obtained.

(¹H NMR (CDCl₃, δ in ppm): 3.98 (s, 3H); 7.47 (d, 1H); 7.84 (d, 1H);10.48 (s, 1H).)

Step f) Methyl 2,4-dichloro-3-hydroxycarbonylbenzoate

At 5° C., 5.9 g (0.043 mol) of sodium dihydrogen phosphate monohydratein 70 ml of water, 20.5 g (0.181 mol) of 30% strength hydrogen peroxidesolution and 27.3 g (0.241 mol) of 80% strength sodium chlorite solutionwere added in succession to a solution of 40.0 g (0.172 mol) of methyl2,4-dichloro-3-formylbenzoate and 500 ml of acetonitrile. The reactionsolution was stirred for 1 hour at 5° C. and for 12 hours at roomtemperature. Subsequently, the pH was adjusted to 1 with 10% strengthhydrochloric acid and 500 ml of 40% strength sodium hydrogen sulfitesolution were added. After stirring for 1 hour at room temperature, theaqueous phase was extracted three times with ethyl acetate and thecombined organic phases were washed with 1.0 l of 10% strength sodiumhydrogen sulfite solution and then dried. Removal of the solvent bydistillation gave 40.0 g of methyl2,4-dichloro-3-hydroxycarbonylbenzoate. (¹H NMR (d⁶-DMSO, δ in ppm):3.90 (s, 3H); 7.69 (d, 1H); 7.89 (d, 1H).)

Step g) Methyl 3-chlorocarbonyl-2,4-dichlorobenzoate

2 drops of dimethylformamide and 11.90 g (0.1 mol) of thionyl chloridewere added to a solution of 5.00 g (0.02 mol) of methyl2,4-dichloro-3-hydroxycarbonylbenzoate and 50 ml of dry toluene. Thesolution was heated under reflux for 4 hours. Removal of the solvent bydistillation gave 5.35 g of methyl3-chlorocarbonyl-2,4-dichlorobenzoate.

Step h) Methyl 2,4-dichloro-3-methoxyaminocarbonylbenzoate

4.60 g (0.045 mol) of triethylamine and 3.75 g (0.045 mol) ofO-methylhydroxylamine hydrochloride were added to a solution of 5.35 g(0.02 mol) of methyl 3-chlorocarbonyl-2,4-dichlorobenzoate and 100 ml ofdichloromethane. After stirring for 12 hours at room temperature, thereaction solution was washed with dilute phosphoric acid, dried andconcentrated. The residue that was obtained was triturated with diethylether. This gave 4.80 g of methyl2,4-dichloro-3-methoxyaminocarbonylbenzoate.

(mp.: 162-164° C.)

Step i) Methyl2,4-dichloro-3-(1′-methoxyimino-1′-(methoxy)methyl)benzoate (compound3.09)

A mixture of 16.0 g (0.058 mol) of methyl2,4-dichloro-3-methoxyaminocarbonylbenzoate and 10.1 g (0.073 mol) ofpotassium carbonate in 300 ml of dimethylformamide was stirred at roomtemperature for 30 minutes. 11.0 g (0.087 mol) of dimethyl sulfate werethen added, the mixture was stirred for 12 hours at room temperature,and a further 11.0 g of dimethyl sulfate were added. The reactionmixture was heated to 60° C. for 6 hours, cooled and stirred into 2 l ofice-water. The aqueous phase was then extracted with ethyl acetate, thecombined organic phases were dried and the solvent was distilled offunder reduced pressure. Silica gel chromatography of the residue(eluent:toluene/ethyl acetate=9/1) afforded 2.0 g of methyl2,4-dichloro-3-(1′-methoxyimino-1-(methoxy)methyl)benzoate.

(¹H NMR (CDCl₃, δ in ppm): 3.43 (s, 3H); 3.58 (s, 3H); 3.92 (s, 3H);7.35 (d, 1H); 7.82 (d, 1H).)

Step j) 2,4-Dichloro-3-(1′-methoxyimino-1′-(methoxy)methyl)benzoic acid(compound 3.10)

A solution of 2.20 g (0.008 mol) of methyl2,4-dichloro-3-(1′-methoxyimino-1l-(methoxy)methyl)benzoate and 3.00 g(0.075 mol) of sodium hydroxide in 50 ml of water was stirred at 80° C.for 2 hours. After cooling, the reaction mixture was stirred into 200 mlof ice-water and adjusted to pH=1 with concentrated hydrochloric acid.The aqueous phase was extracted with ethyl acetate and the combinedorganic phases were dried and concentrated under reduced pressure. 2.10g of 2,4-dichloro-3-(1l-methoxyimino-1′-(methoxy)methyl)benzoic acidwere obtained.

¹H NMR (d⁶-DMSO, δ in ppm): 3.53 (s, 3H); 3.72 (s, 3H); 7.74 (d, 1H);7.95 (d, 1H).)

Step k) 2,4-Dichloro-3-(1′-methoxyimino-1-(methoxy)methyl)benzoylchloride (compound 3.14)

A solution of 2.10 g (0.0076 mol) of2,4-dichloro-3-(1′-(methoxy)imino-1′-methoxymethyl)benzoic acid and20.00 g of thionyl chloride in 50 ml of dry toluene was stirred at 80°C. for 2 hours. Removal of the solvent under reduced pressure afforded2.25 g of 2,4-dichloro-3-(1′-methoxyimino-1′-(methoxy)methyl)benzoylchloride

Methyl 2,4-dichloro-3-propoxyaminocarbonylbenzoate

At 30° C., 10.7 g (0.04 mol) of methyl3-chlorocarbonyl-2,4-dichlorobenzoate in 100 ml of methylene chloridewere slowly added dropwise to a solution of 4.50 g (0.04 mol) ofO-propylhydroxylamine hydrochloride and 4.05 g (0.04 mol) oftriethylamine in 200 ml of methylene chloride. After stirring for 2hours at room temperature, the reaction mixture was washed with dilutephosphoric acid, dried and concentrated. The resulting residue waschromatographed over silica gel (eluent:toluene/ethyl acetate=9/1).11.50 g.of methyl 2,4-dichloro-3-propoxyaminocarbonylbenzoate wereobtained.

(mp.: 80-81° C.)

Methyl 3-(4-chlorobenzyloxyaminocarbonyl)-2,4-dichloro-benzoate

At about 30° C., 10.70 g (0.04 mol) of methyl3-chlorocarbonyl-2,4-dichlorobenzoate in 50 ml of methylene chloridewere slowly added dropwise to a solution of 7.76 g (0.04 mol) ofO-(4-chlorobenzyl)hydroxylamine hydrochloride and 4.05 g (0.04 mol) oftriethylamine in 200 ml of methylene chloride. After stirring for 12hours at room temperature, the reaction mixture was washed with dilutephosphoric acid, dried and concentrated. Trituration of the residue withdiethyl ether gave 19.00 g of methyl3-(4-chlorobenzyloxyaminocarbonyl)-2,4-dichlorobenzoate.

(mp.: 120-121° C.)

3-(1′-Methoxyiminoeth-1′-yl)-2-methyl-4-methylsulfonylbenzoic acid(Compound 3.22)

Step a) 3-(1′-Methoxyiminoeth-1′-yl)-2-methylaniline

50.0 g (0.335 mol) of 3-amino-2-methylacetophenone, 66.3 g (0.838 mol)of pyridine and 42.0 g (0.503 mol) of O-methylhydroxylaminehydrochloride were stirred at room temperature in 400 ml of ethanol. Thesolvent was removed and the residue was taken up in methylene chloride,washed with water, dried and concentrated. This gave 54.0 g (91% oftheory) of 3-(1′-methoxyiminoeth-1′-yl)-2-methylaniline.

Step b) 3-(1′-Methoxyiminoeth-1′-yl)-2-methyl-4-thiocyanatoaniline

At from −20 to −15° C., 50.9 g (0.319 mol) of bromine were addeddropwise to 54.0 g (0.303 mol) of3-(1′-methoxyiminoeth-1′-yl)-2-methylaniline, 49.3 g (0.479 mol) ofsodium bromide and 77.5 g (0.956 mol) of sodium thiocyanate in 300 ml ofmethanol. The mixture was stirred at this temperature for 30 minutes,the insoluble components were filtered off with suction, the filtratewas admixed with ethyl acetate and the pH was adjusted to 8 usingaqueous sodium bicarbonate solution. The organic phase was separated offand the remaining aqueous phase was extracted repeatedly with ethylacetate. The combined organic phases were then washed with water, driedand concentrated. This gave 67.3 g (95% of theory) of3-(1′-methoxyiminoeth-1′-yl)-2-methyl-4-thiocyanatoaniline.

Step c) 3-(1′-Methoxyiminoeth-1′-yl)-2-methyl-4-methylthioaniline

At from 20 to 30° C., 67.3 g (0.286 mol) of3-(1-methoxyiminoeth-1′-yl)-2-methyl-4-thiocyanatoaniline in 600 ml ofmethanol were added dropwise to 40.4 g (0.315 mol) of sodium sulfide in200 ml of water. The mixture was stirred at room temperature for 3 hoursand 45.1 g (0.318 mol) of methyl iodide in 200 ml of methanol were thenadded, again at from 20 to 30° C. The mixture was subsequently stirredat room temperature for 12 hours, the solvent was removed and theresidue was taken up in water and extracted repeatedly with ethylacetate. The combined organic phases were then washed with water, driedand concentrated and the resulting residue was digested withn-hexane/methyl tert-butyl ether. This gave 43.2 g (67% of theory) of3-(1′-methoxyiminoeth-1′-yl)-2-methyl-4-methylthioaniline.

(mp.: 83-89° C.)

Step d) 6-Bromo-2-(1′-methoxyiminoeth-1′-yl)-3-methylthiotoluene

At room temperature, 9.23 g of 47% strength hydrobromic acid were addeddropwise to 3.00 g (13.4 mmol) of3-(1′-methoxyiminoeth-1′-yl)-2-methyl-4-methylthioaniline in 13.40 g ofglacial acetic acid. 9.23 g of water were subsequently added, themixture was stirred at room temperature for 10 minutes and 0.92 g (13.4mmol) of sodium nitrite in 1.9 ml of water was added at from −5 to 0° C.At 0° C., the resulting reaction mixture was then added dropwise to 1.92g (13.4 mmol) of copper(I) bromide in 6 ml of 47% strength hydrobromicacid. The mixture was stirred at room temperature for 12 hours, thenpoured into ice-water and extracted with methylene chloride. The organicphase was then washed with sodium sulfite solution and water and driedand the solvent was removed. This gave 2.50 g (65% of theory) of6-bromo-2-(1′-methoxyiminoeth-1′-yl)-3-methylthiotoluene.

Step e) 6-Bromo-2-(1′-methoxyiminoeth-1′-yl)-3-methylsulfonyltoluene

Over a period of 96 hours, a total of 7.0 g (34.80 mmol) ofm-chloroperbenzoic acid were added a little at a time to 2.5 g (8.71mmol) of 6-bromo-2-(1′-methoxyimino-1′-yl)-3-methylthiotoluene [sic] in50 ml of methylene chloride. The solvent was removed and the residue wastaken up in an organic solvent, washed a [sic] sodium carbonatesolution, sodium sulfite solution and water, dried and concentrated. Theresidue was then chromatographed over silica gel (eluent:toluene/ethylacetate). This gave 0.8 g (29% of theory) of6-bromo-2-(1′-methoxyiminoeth-1′-yl)-3-methylsulfonyltoluene.

Step f) 3-(1′-Methoxyiminoeth-1′-yl)-2-methyl-4-methylsulfonylbenzoicacid

0.77 g (2.41 mmol) of6-bromo-2-(1′-methoxyiminoeth-1′-yl)-3-methylsulfonyltoluene, 0.03 g(0.1 mmol) of palladium acetate, 0.14 g (0.49 mmol) oftricyclohexylphosphine, 0.10 g (2.4 mmol) of lithium chloride and 0.49 g(4.81 mmol) of triethylamine were suspended in 37.5 ml of toluene and17.5 ml of water and gassed at 140° C. and a pressure of 20 bar for 36hours. After cooling, the insoluble particles were then separated off,the organic phase was extracted with water (which had been admixed with1 ml of triethylamine) and the resulting aqueous phase was adjusted topH=1 using hydrochloric acid and extracted with methylene chloride. Thisorganic phase was dried and concentrated. This gave 0.62 g (90% oftheory) of 3-(1′-methoxyiminoeth-1′-yl)-2-methyl-4-methylsulfonylbenzoicacid.

In addition to the compounds described above, further benzoic acidderivatives of the formula IIIa which were prepared or are preparable ina similar manner are listed in Table 3 below.

TABLE 3 IIIa

mp. [° C.] No. X R¹ R² R³ R⁴ R¹⁷ ¹H NMR [ppm] 3.01 O SO₂CH₃ Cl H C₂H₅OCH₃ 1.34(t, 3H); 3.29(s, 3H); 3.98(s, 3H); 4.26(q, 2H); 7.91(d, 1H);8.10(d, 1H); 8.38(s, 1H) 3.02 O Cl Cl H CH₃ OCH₃ 55-57 3.03 O Cl Cl HC₂H₅ OCH₃ 1.35(t, 3H); 3.93(s, 3H); 4.27(q, 2H); 7.42(d, 1H); 7.69(d,1H); 8.24(s, 1H) 3.04 O SO₂CH₃ Cl H C₂H₅ OH 155-160 3.05 O Cl Cl H C₂H₅OH 120-123 3.06 O Cl Cl H CH₃ OH 168-169 3.07 O Cl Cl H CH₂C≡CH OH155-160 3.08 O Cl Cl OC₂H₅ n-C₃H₇ OH 105-106 3.09 O Cl Cl OCH₃ CH₃ OCH₃3.43(s, 3H); 3.58(s, 3H); 3.92(s, 3H); 7.35(d, 1H); 7.82(d, 1H) 3.10 OCl Cl OCH₃ CH₃ OH 3.53(s, 3H); 3.72(s, 3H); 7.74(d, 1H); 7.95(d, 1H)3.11 O Cl Cl OCH₃ CH₂-4-Cl—C₆H₄ OH 3.55(s, 3H); 5.08(s, 2H);7.18-7.30(m, 2H); 7.36(d, 1H); 8.03(d, 1H); 9.14(s, br., 1H) 3.12 O ClCl OCH₃ n-C₃H₇ OCH₃ 47-48 3.13 O Cl Cl OC₂H₅ n-C₃H₇ OCH₃ 48-50 3.14 O ClCl OCH₃ CH₃ Cl 3.15 O SO₂CH₃ Cl H CH₂C₆H₅ OCH₃ 95-100 3.16 O SO₂CH₃ Cl HCH₂C₆H₅ OH 115-120 3.17 O SO₂CH₃ Cl H CH₂-3-thienyl OCH₃ 90-95 3.18 OSO₂CH₃ Cl H CH₃ OCH₃ 95-100 3.19 O SO₂CH₃ Cl H CH₃ OH 180-185 3.20 OSO₂CH₃ Cl H CH₂-3-thienyl OH 95-100 3.21 O SO₂CH₃ Cl CH₃ CH₃ OH 3.22 OSO₂CH₃ CH₃ CH₃ CH₃ OH oil

The 2-benzoylcyclohexane-1,3-diones of the formula I and theiragriculturally useful salts are suitable, both in the form of isomermixtures and in the form of the pure isomers, as herbicides. Theherbicidal compositions comprising compounds of the formula I controlvegetation on non-crop areas very efficiently, especially at high ratesof application. They act against broad-leaved weeds and grass weeds incrops such as wheat, rice, maize, soya and cotton without causing anysignificant damage to the crop plants. This effect is mainly observed atlow rates of application.

Depending on the application method in question, the compounds of theformula I, or compositions comprising them, can additionally be employedin a further number of crop plants for eliminating undesirable plants.Examples of suitable crops are the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis,Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napusvar. napus, Brassica napus var. napobrassica, Brassica rapa var.silvestris, Camellia sinensis, Carthamus tinctorius, Caryaillinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffeacanephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucuscarota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypiumhirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypiumvitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare,Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linumusitatissimum, Lycopersicon lycopersicum, Malus spec., Manihotesculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica),Olea europaea, Oryza sativa , Phaseolus lunatus, Phaseolus vulgaris,Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica,Pyrus communis, Ribes sylestre [sic], Ricinus communis, Saccharumofficinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s.vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum,Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

In addition, the compounds I may also be used in crops which toleratethe action of herbicides owing to breeding, including geneticengineering methods.

The compounds of the formula I, or the compositions comprising them, canbe used for example in the form of ready-to-spray aqueous solutions,powders, suspensions, also highly-concentrated aqueous, oily or othersuspensions or dispersions, emulsions, oil dispersions, pastes, dusts,materials for spreading, or granules, by means of spraying, atomizing,dusting, spreading or pouring. The use forms depend on the intendedaims; in any case, they should guarantee the finest possibledistribution of the active ingredients according to the invention.

The herbicidal compositions comprise a herbicidally active amount of atleast one compound of the formula I or an agriculturally useful salt ofI and auxiliaries conventionally used in the formulation of cropprotection agents.

Suitable inert auxiliaries are essentially: mineral oil fractions ofmedium to high boiling point, such as kerosene and diesel oil,furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffin,tetrahydronaphthalene, alkylated naphthalenes and their derivatives,alkylated benzenes and their derivatives, alcohols such as methanol,ethanol, propanol, butanol and cyclohexanol, ketones such ascyclohexanone, strongly polar solvents, e.g. amines such asN-methylpyrrolidone, and water.

Aqueous use forms can be prepared from emulsion concentrates,suspensions, pastes, wettable powders or water-dispersible granules byadding water. To prepare emulsions, pastes or oil dispersions, thesubstrates [sic], either as such or dissolved in an oil or solvent, canbe homogenized in water by means of a wetting agent, tackifier,dispersant or emulsifier. Alternatively, it is possible to prepareconcentrates comprising active compound, wetting agent, tackifier,dispersant or emulsifier and, if desired, solvent or oil, which aresuitable for dilution with water.

Suitable surfactants (adjuvants) are the alkali metal salts, alkalineearth metal salts and ammonium salts of aromatic sulfonic acids, e.g.ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, andof fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, laurylether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-,hepta- and octadecanols, and also of fatty alcohol glycol ether,condensates of sulfonated naphthalene and its derivatives withformaldehyde, condensates of naphthalene, or of the naphthalenesulfonicacids with phenol and formaldehyde, polyoxyethylene octylphenol ether,ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl ortributylphenyl polyglycol ether, alkylaryl polyether alcohols,isotridecyl alcohol, fatty alcohol/ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylenealkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters,lignin-sulfite waste liquors or methylcellulose.

Powders, materials for spreading and dusts can be prepared by mixing orgrinding the active compounds together with a solid carrier.

Granules, e.g. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active ingredients to solidcarriers. Solid carriers are mineral earths, such as silicas, silicagels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers such asammonium sulfate, ammonium phosphate and ammonium nitrate, ureas, andproducts of vegetable origin, such as cereal meal, tree bark meal, woodmeal and nutshell meal, cellulose powders, or other solid carriers.

The concentrations of the active compounds I in the ready-to-usepreparations can be varied within wide ranges. In general, theformulations comprise approximately from 0.001 to 98% by weight,preferably 0.01 to 95% by weight of at least one active compound. Theactive compounds are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

The formulation examples which follow illustrate the preparation of thecompounds I according to the invention:

I. 20 parts by weight of the compound No. 2.01 are dissolved in amixture composed of 80 parts by weight of alkylated benzene, 10 parts byweight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleicacid N-monoethanolamide, 5 parts by weight of calciumdodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol ofethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000parts by weight of water and finely distributing it therein gives anaqueous dispersion which comprises 0.02% by weight of the activecompound.

II. 20 parts by weight of the compound No. 2.03 are dissolved in amixture composed of 40 parts by weight of cyclohexanone, 30 parts byweight of isobutanol, 20 parts by weight of the adduct of 7 mol ofethylene oxide to 1 mol of isooctylphenol and 10 parts by weight of theadduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring thesolution into 100,000 parts by weight of water and finely distributingit therein gives an aqueous dispersion which comprises 0.02% by weightof the active compound.

III. 20 parts by weight of the active compound No. 2.05 are dissolved ina mixture composed of 25 parts by weight of cyclohexanone, 65 parts byweight of a mineral oil fraction of boiling point 210 to 280° C. and 10parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol ofcastor oil. Pouring the solution into 100,000 parts by weight of waterand finely distributing it therein gives an aqueous dispersion whichcomprises 0.02% by weight of the active compound.

IV. 20 parts by weight of the active compound No. 2.07 are mixedthoroughly with 3 parts by weight of sodiumdiisobutylnaphthalene-α-sulfonate, 17 parts by weight of the sodium saltof a lignosulfonic acid from a sulfite waste liquor and 60 parts byweight of pulverulent silica gel, and the mixture is ground in a hammermill. Finely distributing the mixture in 20,000 parts by weight of watergives a spray mixture which comprises 0.1% by weight of the activecompound.

V. 3 parts by weight of the active compound No. 2.10 are mixed with 97parts by weight of finely divided kaolin. This gives a dust whichcomprises 3% by weight of active compound.

VI. 20 parts by weight of the active compound No. 2.14 are mixedintimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8parts by weight of fatty alcohol polyglycol ether, 2 parts by weight ofthe sodium salt of a phenol/urea/formaldehyde condensate and 68 parts byweight of a paraffinic mineral oil. This gives a stable oily dispersion.

VII. 1 part by weight of the compound No. 2.06 is dissolved in a mixturecomposed of 70 parts by weight of cyclohexanone, 20 parts by weight ofethoxylated isooctylphenol and 10 parts by weight of ethoxylated castoroil. This gives a stable emulsion concentrate.

VIII. 1 part by weight of the compound No. 2.09 is dissolved in amixture [lacuna] of 80 parts by weight of cyclohexanone and 20 parts byweight of Wettol® EM 31 (nonionic emulsifier based on ethoxylated castoroil). This gives a stable emulsion concentrate.

The active compounds of the formula I or the herbicidal compositions canbe applied pre- or post-emergence. If the active compounds are less welltolerated by certain crop plants, application techniques may be used inwhich the herbicidal compositions are sprayed, with the aid of thespraying equipment, in such a way that they come into as little contactas possible, if any, with the leaves of the sensitive crop plants, whilethe active ingredients reach the leaves of undesirable plants growingunderneath, or the bare soil surface (post-directed, lay-by).

To widen the spectrum of action and to achieve synergistic effects, thecompounds of the formula I may be mixed with a large number ofrepresentatives of other herbicidal or growth-regulating activeingredient groups and then applied concomitantly. Suitable componentsfor mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles,amides, aminophosphoric acid and its derivatives, aminotriazoles,anilides, aryl-/hetaryl-oxyalkanoic acids and their derivatives, benzoicacid and its derivatives, benzothiadiazinones,2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones,benzylisoxazolidinones, meta-CF₃-phenyl derivatives, carbamates,quinolinecarboxylic acid and its derivates, chloroacetanilides,cyclohexenone oxime ether derivatives, diazines, dichloropropionic acidand its derivatives, dihydrobenzofurans, dihydrofuran-3-ones,dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls,halocarboxylic acids and their derivatives, ureas, 3-phenyluracils,imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides,oxadiazoles, oxiranes, phenols, aryloxy- and hetaryloxyphenoxypropionicesters, phenylacetic acid and its derivatives, phenylpropionic acid andits derivatives, pyrazoles, phenylpyrazoles, pyridazines,pyridinecarboxylic acid and its derivatives, pyrimidyl ethers,sulfonamides, sulfonylureas, triazines, triazinones, triazolinones,triazolecarboxamides and uracils.

It may furthermore be advantageous to apply the compounds I, alone or incombination with other herbicides, in the form of a mixture with othercrop protection agents, for example together with agents for controllingpests or phytopathogenic fungi or bacteria. Also of interest is themiscibility with mineral salt solutions, which are employed for treatingnutritional and trace element deficiencies. Non-phytotoxic oils and oilconcentrates may also be added.

The rates of application of active compound I are from 0.001 to 3.0,preferably 0.01 to 1.0, kg/ha of active substance (a.s.), depending onthe control target, the season, the target plants and the growth stage

Use Examples

The herbicidal activity of the 2-benzoylcyclohexane-1,3-diones of theformula I was demonstrated by the following greenhouse experiments:

The culture containers used were plastic flowerpots containing loamysoil with approximately 3.0% of humus as the substrate. The seeds of thetest plants were sown separately for each species.

For the pre-emergence treatment, the active compounds, which had beensuspended or emulsified in water, were applied directly after sowing bymeans of finely distributing nozzles. The containers were irrigatedgently to promote germination and growth and subsequently covered withtranslucent plastic hoods until the plants had rooted. This cover causes[sic] uniform germination of the test plants, unless this was adverselyaffected by the active ingredients.

For the post-emergence treatment, the test plants were first grown to aplant height of 3 to 15 cm, depending on the plant habit, and only thentreated with the active compounds which had been suspended or emulsifiedin water. The test plants for this purpose were either sown directly andgrown in the same containers, or they were first grown separately asseedlings and transplanted into the test containers a few days prior totreatment. The rate of application for the post-emergence treatment was0.125.or 0.0625 kg/ha of a.s. (active substance).

Depending on the species, the plants were kept at 10-25° C. or 20-35° C.The test period extended over 2 to 4 weeks. During this time, the plantswere tended, and their response to the individual treatments wasevaluated.

Evaluation was carried out using a scale from 0 to 100. 100 means noemergence of the plants, or complete destruction of at least the aerialparts, and 0 means no damage, or normal course of growth.

The plants used in the greenhouse experiments belonged to the followingspecies:

Scientific name Common name Chenopodium album lambsquarters (goosefoot)Echinochloa crus galli barnyardgrass Sinapis alba white mustard Zea maysmaize

At application rates of 0.125 or 0.0625 kg/ha (of a.s.), the compound2.07 (Table 2) exhibited a very good activity against the abovementionedmono- and dicotyledonous harmful plants when applied post-emergence andwas well tolerated in maize.

We claim:
 1. 2-Benzoylcyclohexane-1,3-diones of the formula I

where: R¹ and R² are each hydrogen, nitro, halogen, cyano, thiocyanato,C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl,C₂-C₆-alkynyl, —OR⁵, —OCOR⁶, —OSO₂R⁶, —SH, —S(O)_(n)R⁷, —SO₂OR⁵,—SO₂NR⁵R⁸, —NR⁸SO₂R⁶ or —NR⁸COR⁶; R³ is hydrogen, cyano, C₁-C₆-alkyl,C₁-C₆-haloalkyl, —OR⁷, —SR⁷ or —NR⁷R¹⁰; R⁴ is hydrogen, C₁-C₆-alkyl,C₃-C₆-cycloalkyl, C₃-C₆-alkenyl, C₄-C₆-cycloalkenyl, C₃-C₆-alkynyl,—COR⁹, —CO₂R⁹, —COSR⁹ or —CONR⁸R⁹, where the alkyl, cycloalkyl, alkenyl,cycloalkenyl and alkynyl radicals mentioned and R⁹ of the radicals—COR⁹, —CO₂R⁹, —COSR⁹ and —CONR⁸R⁹ may be partially or fully halogenatedand/or carry one to three of the following groups: hydroxyl, mercapto,amino, cyano, R¹⁰, —OR¹⁰, —SR¹⁰, —NR⁸R¹⁰, ═NOR¹⁰, —OCOR¹⁰, —SCOR¹⁰,—NR⁸COR¹⁰, —CO₂R¹⁰, —COSR¹⁰, —CONR⁸R¹⁰, C₁-C₄-alkyliminooxy,C₁-C₄-alkoxyamino, C₁-C₄-alkylcarbonyl,C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, C₁-C₄-alkylsulfonyl, heterocyclyl,heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy andhetaryloxy, where the last eight radicals mentioned may in turn besubstituted; X is oxygen or NR⁸; n is 0, 1 or 2; R⁵ is hydrogen,C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₂-C₆-alkyl, C₃-C₆-alkenyl orC₃-C₆-alkynyl; R⁶ is C₁-C₆-alkyl or C₁-C₆-haloalkyl; R⁷ is C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₂-C₆-alkyl, C₃-C₆-alkenyl orC₃-C₆-alkynyl; R⁸ is hydrogen or C₁-C₆-alkyl; R⁹ is C₁-C₆-alkyl,C₃-C₆-alkenyl, C₃-C₆-alkynyl, phenyl or benzyl; R¹⁰ is C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl; Q is acyclohexane-1,3-dione ring attached in position 2 with or withoutsubstitution; and agriculturally useful salts thereof. 2.2-Benzoylcyclohexane-1,3-diones of the formula I as claimed in claim 1in which Q is a cyclohexane-1,3-dione ring of the formula II

attached in position 2 where R¹¹, R¹², R¹⁴ and R¹⁶ are each hydrogen orC₁-C₄-alkyl; R¹³ is hydrogen, C₁-C₄-alkyl or C₃-C₄-cycloalkyl, where thelast two groups may carry one to three of the following substituents:halogen, C₁-C₄-alkylthio or C₁-C₄-alkoxy; or is tetrahydropyran-2-yl,tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl,tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl,1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl,1,3-dithiolan-2-yl or 1,3-dithian-2-yl, where the last 6 radicalsmentioned may be substituted by one to three C₁-C₄-alkyl radicals; R¹⁵is hydrogen, C₁-C₄-alkyl or C₁-C₆-alkoxycarbonyl; or R¹³ and R¹⁶together form a π-bond or a three- to six-membered carbocyclic ring; orthe CR¹³R¹⁴ unit is replaced by C═O.
 3. 2-Benzoylcyclohexane-1,3-dionesof the formula I as claimed in claim 1, where R¹ is nitro, halogen,cyano, thiocyanato, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, —OR⁵ or—S(O)_(n)R⁷; R² is hydrogen or one of the radicals mentioned above underR¹.
 4. 2-Benzoylcyclohexane-1,3-diones of the formula Ia

where the variables R¹ to R⁴, X and Q are each as defined under claim 1.5. A process for preparing 2-benzoylcyclohexane-1,3-diones of theformula I as claimed in claim 1, which comprises acylating anunsubstituted or substituted cyclohexane-1,3-dione Q with an activatedcarboxylic acid IIIα or with a carboxylic acid IIIβ,

where the variables R¹ to R⁴ and X are each as defined under claim 1 andL is a nucleophilically displaceable leaving group, and rearranging theacylation product in the presence or absence of a catalyst to thecompounds I.
 6. A composition comprising a herbicidally active amount ofat least one compound of the formula I or an agriculturally useful saltof I as claimed in claim 1, and auxiliaries conventionally used in theformulation of crop protection agents.
 7. A process for preparingherbicidally active compositions as claimed in claim 6, which comprisesmixing the herbicidally active amount of the at least one compound offormula I or the agriculturally useful salt and auxiliariesconventionally used in the formulation of crop protection agents.
 8. Amethod for controlling undesirable vegetation, which comprises allowinga herbicidally active amount of at least one compound of the formula Ior an agriculturally useful salt of I as claimed in claim 1 to act onplants, their habitat and/or on seeds.
 9. A benzoic acid compound offormula IIIa,

wherein R¹ is nitro, halogen, cyano, thiocyanato, C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynylor —S(O)_(n)R⁷; R² is nitro, halogen, cyano, thiocyanato, C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,—OR⁵ or —S(O)_(n)R⁷; R³ is hydrogen, cyano, C₁-C₆-alkyl,C₁-C₆-haloalkyl, —OR⁷, —SR⁷ or —NR⁷R¹⁰; R⁴ is C₁-C₆-alkyl,C₃-C₆-cycloalkyl, C₃-C₆-alkenyl, C₄-C₆-cycloalkenyl, C₃-C₆-alkynyl,—COR⁹, —CO₂R⁹, —COSR⁹ or —CONR⁸R⁹, where the alkyl, cycloalkyl, alkenyl,cycloalkenyl and alkynyl radicals mentioned and R⁹ of the radicals—COR⁹, —CO₂R⁹, —COSR⁹ and —CONR⁸R⁹ may be partially or fully halogenatedand/or carry one to three of the following groups: hydroxyl, mercapto,amino, cyano, R¹⁰, —OR¹⁰, —SR¹⁰, —NR⁸R¹⁰, ═NOR¹⁰, —OCOR¹⁰, —SCOR¹⁰,—NR⁸COR¹⁰, —CO₂R¹⁰, —COSR¹⁰, —CONR⁸R¹⁰, C₁-C₄-alkyliminooxy,C₁-C₄-alkoxyamino, C₁-C₄-alkylcarbonyl,C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, C₁-C₄-alkylsulfonyl, heterocyclyl,heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy andhetaryloxy, where the last eight radicals mentioned may in turn besubstituted; X is oxygen or NR⁸; n is 0, 1 or 2; R⁵ is hydrogen,C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₂-C₆-alkyl, C₃-C₆-alkenyl orC₃-C₆-alkynyl; R⁷ is C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆-alkoxy-C₂-C₆-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl; R⁸ is hydrogenor C₁-C₆-alkyl; R⁹ is C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, phenylor benzyl; R¹⁰ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl orC₃-C₆-alkynyl; R¹⁷ is hydroxyl or a radical that can be removed byhydrolysis.
 10. The compound of formula IIIa as claimed in claim 9,where R¹⁷ is halogen, hydroxyl or C₁-C₆-alkoxy.